SUEMENTARY INRMATIN - Nature Research · Electrospray Ionization (ESI+) spectra were performed using a time-of-flight (TOF) mass analyzer. Data are reported in the form of m/z (intensity

NATURE CHEMISTRY | www.nature.com/naturechemistry 1

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.2141

Cresswell, Eey & Denmark S1

Catalytic, Stereospecific Syn-Dichlorination of Alkenes

Alexander J. Cresswell, Stanley T.-C. Eey and Scott E. Denmark*

Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801

SUPPORTING INFORMATION

TABLE OF CONTENTS PAGE

General Experimental

Literature Preparations

Preparation of Reagents

Preparation of Alkenes

Experimental Procedures


Preparation of Diaryl Diselenides

General Procedure I: Reaction Development with Cyclohexene (Table 1)

General Procedure II: Survey of Lewis Base Additives with (E)-1-Benzyloxyl-4-

hexene (17) (Table 2)

General Procedure III: Survey of Diaryl Diselenides with (E)-1-Benzyloxyl-4-


Table S1. Preliminary Survey of Reaction Generality

General Procedure IV: Preliminary Survey of Reaction Generality (Table S1)

General Procedure V: Control Experiments with (E)-1-Benzyloxyl-4-hexene (17)

General Procedure VI: NMR Spectroscopic Studies on Catalytic,

syn-Dichlorination of Volatile Alkenes

General Procedure VII: Catalytic, syn-Dichlorination of Alkenes with 2,6-Lutidine

N-Oxide as Additive (Table 3)

General Procedure VIII: Catalytic, syn-Dichlorination of Allylic Alcohols (Table 3)

Determination of Relative Configurations Within Dichlorides (Table 3)

S3

S6

S6

S6

S30

S33

S39

S45

S48

S49

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S64

S67

S101

S109

Cresswell, Eey & Denmark S1

Catalytic, Stereospecific Syn-Dichlorination of Alkenes

Alexander J. Cresswell, Stanley T.-C. Eey and Scott E. Denmark*

Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801

SUPPORTING INFORMATION

TABLE OF CONTENTS PAGE









General Procedure II: Survey of Lewis Base Additives with (E)-1-Benzyloxyl-4-


General Procedure III: Survey of Diaryl Diselenides with (E)-1-Benzyloxyl-4-





General Procedure VI: NMR Spectroscopic Studies on Catalytic,

syn-Dichlorination of Volatile Alkenes

General Procedure VII: Catalytic, syn-Dichlorination of Alkenes with 2,6-Lutidine

N-Oxide as Additive (Table 3)


Determination of Relative Configurations Within Dichlorides (Table 3)

S3

S6

S6

S6

S30

S33

S39

S45

S48

S49

S62

S64

S67

S101

S109

© 2015 Macmillan Publishers Limited. All rights reserved


SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.2141Cresswell, Eey & Denmark S2

General Procedure IX: anti-Selective Dichlorination of Alkenes with Cl2

Determination of Configurations Within Vinylic Chlorides (Figure 2)

Table of Problematic Substrates

References

NMR Spectra

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Reaction Setup: All reactions were performed in oven (160 °C) and/or flamed-dried

glassware under an atmosphere of dry argon, unless otherwise indicated. All reported reaction

temperatures correspond to internal temperatures measured with a Teflon coated thermocouple.

Room temperature (rt) was approximately 23 °C. “Brine” refers to a saturated solution of sodium

chloride in H2O.

NMR Spectroscopy: 1H and 13C{1H} NMR spectra were recorded on Varian Unity Inova

400 (400 MHz, 1H; 100 MHz, 13C) or 500 (500 MHz, 1H; 126 MHz, 13C) MHz spectrometers.

Acquisition times were 4.096 s for 1H NMR, and 1.024 s for 13C NMR. Variable temperature

(VT) NMR experiments were performed on a Varian Unity Inova 500 MHz spectrometer

equipped with an external FTS cooling unit (set at 0 °C) for temperature control. Spectra are

referenced to residual chloroform (δ = 7.26 ppm, 1H; 77.00 ppm, 13C) or residual acetonitrile (δ =

1.94 ppm, 1H; 1.32 ppm, 13C). Chemical shifts are reported in parts per million (ppm).

Multiplicities are indicated by s (singlet), d (doublet), t (triplet), q (quartet), pent (pentet), and m

(multiplet). Coupling constants, J, are reported in Hertz. Integration is provided and assignments

are indicated. 1H and 13C assignments are corroborated through 2-D NMR experiments (COSY,

HSQC, HMBC). 1-D NOESY experiments were also used to assign relative configuration in

certain cases.

Infrared Spectroscopy: Infrared (IR) spectra were recorded on a Perkin-Elmer FT-IR

system on NaCl plates. Peaks are reported in cm−1 with indicated relative intensities: s (strong,

0–33% T); m (medium, 34–66% T), w (weak, 67–100% T), and br (broad).

Mass Spectrometry: Mass spectrometry (MS) was performed by the University of Illinois

Mass Spectrometry Laboratory. Electron Impact (EI+) spectra were performed at 70 eV using

methane as the carrier gas, with either a double focusing sector field (DFSF) or time-of-flight

(TOF) mass analyzer. Chemical Ionization (CI+) spectra were performed with methane reagent

gas, with either a double focusing sector field (DFSF) or time-of-flight (TOF) mass analyzer.

Electrospray Ionization (ESI+) spectra were performed using a time-of-flight (TOF) mass

analyzer. Data are reported in the form of m/z (intensity relative to the base peak = 100).

Melting Points: Melting points (mp) were determined on a Thomas-Hoover capillary

melting point apparatus in vacuum-sealed capillary tubes and are corrected.

Elemental Analysis: Elemental analysis was performed by the University of Illinois




Microanalysis Laboratory or Robertson Microlit Laboratories (1705 U.S. Highway 46, Suite 1D,

Ledgewood, New Jersey 07852, U.S.A.). Reported data is the average of at least 2 runs.

Distillation: Bulb-to-bulb distillation was performed on a Kugelrohr, with boiling points

(bp) corresponding to uncorrected air-bath temperatures (ABT). A vacuum of 10−5 mm Hg was

achieved using a BOC Edwards SI100 diffusion pump.

Chromatography: Analytical thin-layer chromatography was performed on Merck silica

gel 60 F254 or Merck silica gel 60 RP-18 F254s plates. Visualization was accomplished with UV

light and/or potassium permanganate (KMnO4) solution or ceric ammonium molybdate (CAM)

solution. Retention factor (Rf) values reported were measured using a 10 × 2 cm TLC plate in a

developing chamber containing the solvent system (10 mL) described. Flash column

chromatography was performed using Silicycle SiliaFlash® P60 (40-63 µm particle size, 230-400

mesh) (SiO2) or Woelm’s high porosity grade silica. Unless otherwise specified, “SiO2” refers to

P60 grade silica gel. Automated flash column chromatography was performed on a Teledyne

Isco CombiFlash® Rf 200 using pre-packed silica gel columns.

Solvents: Reaction solvents tetrahydrofuran (THF) (Fisher, HPLC grade), ether (Et2O)

(Fisher, BHT stabilized ACS grade), and dichloromethane (CH2Cl2) (Fisher, unstabilized HPLC

grade) were dried by percolation through two columns packed with neutral alumina under a

positive pressure of argon. Reaction solvent toluene (ACS grade) was dried by percolation

through a column packed with neutral alumina and a column packed with Q5 reactant (supported

copper catalyst for scavenging oxygen) under a positive pressure of argon. Reaction solvent

dimethylformamide (DMF) (Fischer, ACS grade) was dried by percolation through two columns

of activated molecular sieves. Reaction solvent acetonitrile (CH3CN) (ACS grade, amylene

stabilized) was distilled from CaH2 prior to use. Reaction solvent ethanol (absolute, Decon

Laboratories) was used as received. Solvents for filtration, transfers, chromatography, and

recrystallization were benzene (PhH) (Fisher, ACS grade), dichloromethane (CH2Cl2) (ACS

grade, amylene stabilized), ether (Et2O) (Fisher, BHT stabilized ACS grade), ethyl acetate

(EtOAc) (Fisher, ACS grade), hexane (Optima), methyl tert-butyl ether (MTBE) (ACS grade),

methanol (MeOH) (ACS grade), pentane (ACS grade), and petroleum ether (35–60°C, ACS

grade).

Chemicals: Cyclohexene (Aldrich) and cycloheptene (Aldrich) were distilled prior to use.

(Z)-4-Hexen-1-ol (Alfa), benzyl bromide (Eastman), chlorotrimethylsilane (Aldrich), 1,1,2,2-




tetrachloroethane, and triethylamine (Aldrich) were distilled from CaH2 prior to use. Sulfolane

(Aldrich) was distilled from 4Å molecular sieves (powder) prior to use. Dimethyl sulfoxide

(DMSO) (Fischer) was dried over 4Å molecular sieves (pellets) prior to use. N-Fluoropyridinium

tetrafluoroborate (11) (TCI), 3-buten-1-ol (Aldrich), 4-N,N′-dimethylaminopyridine (DMAP)

(Aldrich), acetic anhydride (Fisher), benzyltriethylammonium chloride (Oakwood), diphenyl

diselenide (TCI), bis(2-nitrophenyl) diselenide (Acros), selenium powder (Aldrich), imidazole

(Aldrich), (E)-4-octene (GFS Organic), tri-iso-propylsilyl chloride (TIPSCl) (Gelest), tert-

butyldiphenylsilyl chloride (TBDPSCl) (Gelest), m-chloroperbenzoic acid (m-CPBA) (Acros),

cyclopropanecarboxylic acid (Aldrich), N,N’-dicyclohexylcarbodiimide (DCC) (Alfa), 1,1’-

carbonyldiimidazole (CDI) (Aldrich), benzylmagnesium chloride (Aldrich), N,O-

dimethylhydroxylamine hydrochloride (Alfa), ethylene glycol (Aldrich), p-toluenesulfonic acid

(PTSA) monohydrate (Aldrich), oxalyl chloride (Alfa), benzylamine (TCI), sodium hydride

(Aldrich), di-tert-butyl dicarbonate (Boc2O) (Alfa), potassium phthalimide (Aldrich), Red-Al®

(Aldrich), 4-bromoanisole (Aldrich), 2-bromoanisole (Alfa), tert-butyllithium (Aldrich), N-

chlorosuccinimide (NCS) (Aldrich), and triphenylphosphine (Aldrich) were used as received.






The following compounds were prepared according to literature procedures: 2,6-lutidine

N-oxide (23),1 and bis[3,5-bis(trifluoromethyl)phenyl] diselenide (24).2,3,4


The following compounds were prepared according to literature procedures: (E)-4-hexen-

1-ol,5 ethyl (E)-4-hexenoate (28k),5 3-cyclopenten-1-ylmethanol,6 (E)-7-phenylhept-4-en-1-ol,7

4-(but-3-en-1-yl)-2,2-dimethyl-1,3-dioxolane (28e),8 (E)-[(hex-4-en-1-yloxy)methyl]benzene

(17),5 (E)-5-phenylpent-2-en-1-ol (28u),9 (Z)-5-phenylpent-2-en-1-ol (28v),10 (Z)-4-

(benzyloxy)but-2-en-1-ol (28x),11 and (Z)-6-iodo-2-hexene.12



Preparation of Cyclopent-3-en-1-ylmethyl acetate (28b)

A 100-mL, round-bottomed flask equipped with a magnetic stirrer bar was charged with

4-N,N-dimethylaminopyridine (61.7 mg, 0.50 mmol, 10 mol %) and 3-cyclopenten-1-ylmethanol

(491 mg, 5.00 mmol, 1.0 equiv) then was sealed with a rubber septum and purged with argon via

an inlet needle. CH2Cl2 (25 mL) and triethylamine (1.01 g, 1.39 mL, 10.0 mmol, 2.0 equiv) were

then added sequentially and stirring was commenced. The mixture was cooled in an ice-water

bath and acetic anhydride (1.02 g, 945 µL, 10.0 mmol, 2.0 equiv) was added dropwise via

syringe over ca. 1 min, then the resultant mixture was allowed to warm to rt over 2 h. The

reaction mixture was then transferred to a separatory funnel and brine (10 mL) and H2O (10 mL)

were added. The layers were separated and the aqueous layer was extracted with CH2Cl2 (2 × 10




mL). The combined organic extracts were washed sequentially with sat. aq. NaHCO3 (40 mL)

and sat. aq. CuSO4 (40 mL), then dried (MgSO4), filtered, and concentrated in vacuo (45 °C, 120

mm Hg) to give a colorless oil (1.03 g). Purification via flash column chromatography (40 g

SiO2, 30 mm Ø, wet loaded, 97:3 hexane/MTBE, ca. 5 mL fractions) gave a colorless oil (750

mg). Further purification via Kugelrohr distillation at reduced pressure (20 mm Hg) gave 28b as

a clear, colorless oil (488 mg, 70%).

Data for 28b:

bp: 80 °C (ABT) (20 mm Hg) 1H NMR: (500 MHz, CDCl3)

5.67–5.62 (m, 2 H, HC(1,5)), 3.97 (d, J = 7.3 Hz, 2 H, C(3)CH2OAc), 2.64–2.54 (m,

1 H, HC(3)), 2.52–2.43 (m, 2 H, HC(2,4)), 2.13–2.01 (m, 5 H, HC(2,4), COMe) 13C NMR: (126 MHz, CDCl3)

171.1 (COMe), 129.2 (C(1,5)), 68.1 (C(3)CH2OAc), 35.8 (C(3)), 35.6 (C(2,4)),

20.9 (COMe)

IR: (neat)

3056 (w), 2937 (m), 2850 (m), 1743 (s), 1616 (w), 1467 (w), 1443 (m), 1385 (m),

1365 (m), 1237 (s), 1079 (w), 1036 (m), 978 (w), 952 (w), 905 (w), 828 (w), 773

(w), 679 (m), 632 (w), 773 (w), 679 (m), 632 (w), 605 (w)

MS: (CI+, DFSF)

141.1 ([M+H]+, 0.6), 81.1 ([M–OAc]+, 100)

TLC: Rf 0.13 (95:5 hexane/MTBE) [KMnO4]

HRMS: (CI+, DFSF)

calcd for C8H13O2 ([M+H]+): 141.0916, found: 141.0915




Preparation of tert-Butyl(cyclopent-3-en-1-ylmethoxy)diphenylsilane (28c)

A flame-dried, 50-mL, round-bottomed flask equipped with a magnetic stirrer bar was

charged with 3-cyclopenten-1-ylmethanol (491 mg, 5.00 mmol, 1.0 equiv) and imidazole (518

mg, 7.61 mmol, 1.5 equiv) then was sealed with a rubber septum and purged with argon via an

inlet needle. CH2Cl2 (12.5 mL) was then added and stirring was commenced. tert-

Butyldiphenylsilyl chloride (1.51 g, 1.43 mL, 5.50 mmol, 1.1 equiv) was added dropwise via

syringe and the resultant cloudy mixture was stirred under argon at rt for 16 h. The reaction

mixture was quenched with H2O (20 mL), diluted with CH2Cl2 (10 mL), then was transferred to

a separatory funnel and the layers were separated. The aqueous layer was extracted with CH2Cl2

(2 × 20 mL) and the combined organic extracts were washed with brine (20 mL), dried (MgSO4),

filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a colourless oil.

Purification via flash column chromatography [72 g high porosity grade SiO2, 34 mm Ø, wet

loaded, petroleum ether (900 mL), ca. 20 mL fractions] gave 28c as a clear, colorless oil (1.61 g,

96%). The 1H and 13C NMR spectroscopic data matched that for alternative preparations.13

Data for 28c: 1H NMR: (500 MHz, CDCl3)

δ 7.72–7.66 (m, 4 H, HC(2′,2′′)), 7.47–7.36 (m, 6 H, HC(3′,3′′,4′,4′′)), 5.68–5.64 (m,

2 H, HC(3,4)), 3.59 (d, J = 7.1 Hz, 2 H, HC(6)), 2.62–2.51 (m, 1 H, HC(1)), 2.49–

2.41 (m, 2 H, HC(2,5)), 2.21–2.12 (m, 2 H, HC(2,5)), 1.07 (s, 9 H, Sit-Bu) 13C NMR: (126 MHz, CDCl3)

δ 135.6 (C(2′,2′′)), 134.1 (C(1′,1′′)), 129.6 (C(4′,4′′)), 129.5 (C(3,4)), 127.6

(C(3′,3′′)), 67.7 (C(6)), 39.4 (C(1)), 35.5 (C(2,5)), 26.9 (SiCMe3), 19.3 (SiCMe3)




Preparation of (But-3-en-1-yloxy)(tert-butyl)diphenylsilane (28d)


imidazole (309 mg, 4.50 mmol, 1.5 equiv) and 3-buten-1-ol (225 mg, 3.00 mmol, 1.0 equiv) then

was sealed with a rubber septum and purged with argon via an inlet needle. CH2Cl2 (6.0 mL) was

then added and stirring was commenced. tert-Butyldiphenylsilyl chloride (922 mg, 872 µL, 3.30

mmol, 1.1 equiv) was added via syringe in one portion and the resultant mixture was stirred

under argon at rt for 22 h. The reaction mixture was then transferred to a separatory funnel and

diluted with CH2Cl2 (25 mL), washed sequentially with H2O (10 mL) and brine (10 mL), then

dried (MgSO4), filtered, and concentrated in vacuo (45 °C, ca. 5 mm Hg) to give a colorless oil

(1.14 g). Purification via flash column chromatography (40 g SiO2, 30 mm Ø, wet loaded, 98:2

hexane/MTBE, ca. 5 mL fractions) gave a colorless oil (975 mg). Further purification via

Kugelrohr distillation at reduced pressure (10–5 mm Hg) gave 28d as a clear, colorless oil (931

mg, quant). The 1H and 13C NMR spectroscopic data matched that for alternative preparations.14

Data for 28d:

bp: 125 °C (ABT) (10–5 mm Hg)

1H NMR: (500 MHz, CDCl3)

δ 7.73–7.69 (m, 4 H, HC(4′,4′′)), 7.47–7.38 (m, 6 H, HC(3′,3′′,4′,4′′)), 5.87 (ddt, J =

17.1, 10.2, 6.9 Hz, 1 H, HC(3)), 5.12–5.03 (m, 2 H, HC(4)), 3.75 (t, J = 6.7 Hz, 2 H,

HC(1)), 2.36 (qt, J = 6.7, 1.3 Hz, 2 H, HC(2)), 1.09 (s, 9 H, Sit-Bu) 13C NMR: (126 MHz, CDCl3)

δ 135.6 (C(2′,2′′)), 135.4 (C(3)), 133.9 (C(1′,1′′)), 129.5 (C(4′,4′′)), 127.6 (C(3′,3′′)),

116.4 (C(4)), 63.5 (C(1)), 37.2 (C(2)), 26.8 (SiCMe3), 19.2 (SiCMe3)




Preparation of (Z)-[(Hex-4-en-1-yloxy)methyl]benzene (28h)

A flame-dried, 25-mL, Schlenk flask equipped with a magnetic stirrer bar and water-

jacketed reflux condensor was charged sequentially with (Z)-4-hexen-1-ol (620 mg, 723 µL, 6.00

mmol, 1.0 equiv) and THF (10 mL). The solution was cooled in an ice-water bath and NaH

(washed, 158 mg, 6.60 mmol, 1.1 equiv) was added against a backflow of argon, and the

resultant mixture was stirred in the ice-water bath for 15 min. Benzyl bromide (1.13 g, 785 µL,

6.60 mmol, 1.1 equiv) was then added via syringe in one portion and the resultant mixture was

stirred at reflux for 14 h. After being allowed to cool to rt, the reaction was quenched by addition

of sat. aq. NH4Cl (2.0 mL). H2O (20 mL) and EtOAc (20 mL) were then added and the layers

were separated. The aqueous layer was extracted with EtOAc (2 × 20 mL) and the combined

organic extracts were washed with brine (30 mL) then dried (MgSO4), filtered, and concentrated

in vacuo (45 °C, ca. 5 mm Hg) to give a colorless oil (733 mg). Purification via flash column

chromatography (40 g SiO2, 30 mm Ø, wet loaded, 98:2 hexane/MTBE, ca. 5 mL fractions) gave

a clear, colorless oil (1.13 g). Further purification via Kugelrohr distillation at reduced pressure

(0.01 mm Hg) gave 28h as a clear, colorless oil (1.06 g, 93%, >99:1 dr, contaminated with 2%

regioisomeric terminal alkene impurity). The 1H and 13C NMR spectroscopic data matched that

for alternative preparations.15

Data for 28h:

bp: 100 °C (ABT) (0.01 mm Hg)


δ 7.39–7.33 (m, 4 H, HC(2′,3′)), 7.33–7.27 (m, 1 H, HC(4′)), 5.52–5.44 (m, 1 H,

HC(5)), 5.43–5.36 (m, 1 H, HC(4)), 4.52 (s, 2 H, HC(5′)), 3.49 (t, J = 6.5 Hz, 2 H,

HC(1)), 2.15 (app q, J = 7.4 Hz, 2 H, HC(3)), 1.73–1.66 (m, 2 H, HC(2)), 1.62 (ddt,

J = 6.7, 1.9, 0.9 Hz, 3 H, HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 138.6 (C(1′)), 129.9 (C(4)), 128.3 (C(3′)), 127.6 (C(2′)), 127.5 (C(4′)), 124.4

(C(5)), 72.9 (C(5′)), 69.8 (C(1)), 29.5 (C(2)), 23.4 (C(3)), 12.7 (C(6))




Preparation of (E)-tert-Butyl(hex-4-en-1-yloxy)diphenylsilane (13)


imidazole (309 mg, 4.50 mmol, 1.5 equiv) and (E)-4-hexen-1-ol (300 mg, 353 µL, 3.00 mmol,

1.0 equiv) then was sealed with a rubber septum and purged with argon via an inlet needle.

CH2Cl2 (6.0 mL) was then added and stirring was commenced. tert-Butyldiphenylsilyl chloride

(922 mg, 872 µL, 3.30 mmol, 1.1 equiv) was added via syringe in one portion and the resultant

mixture was stirred under argon at rt for 18.5 h. The reaction mixture was then transferred to a

separatory funnel and diluted with CH2Cl2 (25 mL), washed sequentially with H2O (10 mL) and

brine (10 mL), then dried (MgSO4), filtered, and concentrated in vacuo (45 °C, ca. 5 mm Hg) to

give a colorless oil (1.15 g). Purification via flash column chromatography (40 g SiO2, 30 mm Ø,

99:1 hexane/MTBE, ca. 5 mL fractions) gave a colorless oil (1.00 g). Further purification via

Kugelrohr distillation at reduced pressure (10–5 mm Hg) gave 13 as a clear, colorless oil (985 mg,

97%, >99:1 dr).

Data for 13:

bp: 125 °C (ABT) (10–5 mm Hg) 1H NMR: (500 MHz, CDCl3)

7.71–7.66 (m, 4 H, HC(2′,2′′)), 7.46–7.36 (m, 6 H, HC(3′,3′′,4′,4′′), 5.48–5.36 (m, 2

H, HC(4,5)), 3.67 (t, J = 6.4 Hz, 2 H, HC(1)), 2.12–2.05 (m, 2 H, HC(3)), 1.67–

1.58 (m, 5 H, HC(2,6)), 1.06 (s, 9 H, Sit-Bu) 13C NMR: (125 MHz, CDCl3)

135.5 (C(2′,2′′)), 134.1 (C(1′,1′′)), 130.9 (C(4)), 129.4 (C(4′,4′′)), 127.5 (C(3′,3′′)),

125.0 (C(5)), 63.3 (C(1)), 32.4 (C(2)), 28.8 (C(3)), 26.8 (SiCMe3), 19.2 (SiCMe3),

17.9 (C(6))

IR: (neat)

3134 (w), 3070 (m), 3049 (m), 3016 (m), 2998 (w), 2931 (s), 2857 (s), 2736 (w),

1958 (w), 1888 (w), 1823 (w), 1654 (w), 1589 (w), 1486 (w), 1472 (m), 1462 (w),

1448 (w), 1427 (m), 1389 (w), 1361 (w), 1305 (w), 1260 (w), 1225 (w), 1188 (w),




1111 (s), 1042 (w), 1007 (w), 998 (w), 964 (m), 939 (w), 911 (w), 823 (m), 739 (m),

701 (s), 687 (m), 613 (m)

MS: (CI+, DFSF)

339.2 ([M+H]+, 4), 282.1 (24), 281.1 ([M–t-Bu]+, 100), 269.1 (14), 262.1 (16),

261.1 ([M–Ph]+, 72), 253.1 (27), 239.1 (12), 233.1 (14), 219.1 (10), 199.0 (15),

183.0 (10), 91.1 (23), 83.1 (22), 59.1 (33)


HRMS: (CI+, DFSF)

calcd for C22H31OSi ([M+H]+): 339.2144, found: 339.2128

Preparation of (Z)-tert-Butyl(hex-4-en-1-yloxy)diphenylsilane (28i)


imidazole (309 mg, 4.50 mmol, 1.5 equiv) and (Z)-4-hexen-1-ol (310 mg, 361 µL, 3.00 mmol,




mixture was stirred under argon at rt for 18.5 h. The reaction mixture was then transferred to a

separatory funnel and diluted with CH2Cl2 (25 mL), washed sequentially with H2O (10 mL) and



wet loaded, 99:1 hexane/MTBE, ca. 5 mL fractions) gave a colorless oil (1.06 g). Further

purification via Kugelrohr distillation at reduced pressure (10–5 mm Hg) gave 28i as a clear,

colorless oil (1.02 g, quant, >99:1 dr).

Data for 28i:

bp: 125 °C (ABT) (10–5 mm Hg) 1H NMR: (500 MHz, CDCl3)

7.73–7.69 (m, 4 H, HC(2′,2′′)), 7.47–7.38 (m, 6 H, HC(3′,4′′)), 5.52–5.35 (m, 2 H,




HC(4,5)), 3.71 (t, J = 6.4 Hz, 2 H, HC(1)), 2.17 (q, J = 7.3 Hz, 2 H, HC(3)), 1.68–

1.61 (m, 5 H, HC(2,6)), 1.09 (s, 9 H, Sit-Bu) 13C NMR: (125 MHz, CDCl3)

135.5 (C(2′,2′′)), 134.0 (C(1′,1′′)), 130.1 (C(4)), 129.4 (C(4′,4′′)), 127.5 (C(3′,3′′)),

124.1 (C(5)), 63.4 (C(1)), 32.4 (C(2)), 26.8 (SiCMe3), 23.1 (C(3)), 19.2 (SiCMe3),

12.7 (C(6))

IR: (neat)

3135 (w), 3070 (m), 3049 (w), 3013 (m), 2931 (s), 2858 (s), 2739 (w), 1957 (w),

1886 (w), 1824 (w), 1655 (w), 1589 (w), 1486 (w), 1472 (m), 1462 (w), 1446 (w),

1403 (w), 1389 (w), 1361 (w), 1305 (w), 1259 (w), 1222 (w), 1189 (w), 1111 (s),

1043 (w), 1006 (w), 998 (w), 960 (w), 940 (w), 823 (m), 739 (m), 701 (s), 688 (m),

613 (m)

MS: (CI+, DFSF)

339.2 ([M+H]+, 5), 282.1 (23), 281.1 ([M–t-Bu]+, 100), 262.1 (17), 261.1 ([M–Ph]+,

80), 239.1 (12), 199.0 (15), 83.1 (30)


HRMS: (FAB+, DFSF)


Preparation of (E)-Tri-iso-propyl[(7-phenylhept-4-en-1-yl)oxy]silane (28j)


charged with (E)-7-phenylhept-4-en-1-ol (951 mg, 5.00 mmol, 1.0 equiv) and imidazole (515

mg, 7.56 mmol, 1.5 equiv) then was sealed with a rubber septum and purged with argon via an

inlet needle. CH2Cl2 (12.5 mL) was then added and stirring was commenced. Tri-iso-propylsilyl

chloride (1.08 g, 1.20 mL, 5.61 mmol, 1.1 equiv) was added dropwise via syringe and the

resultant mixture was stirred under argon at rt for 16 h. The reaction mixture was quenched with

H2O (20 mL), diluted with CH2Cl2 (10 mL), then transferred to a separatory funnel and the layers

were separated. The aqueous layer was extracted with CH2Cl2 (2 × 20 mL) and the combined




organic extracts were washed with brine (20 mL), dried (MgSO4), filtered, and concentrated in

vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil. Purification via flash column

chromatography [71 g high porosity grade SiO2, 34 mm Ø, wet loaded, 100:0 → 98:2

hexane/EtOAc (200 and 900 mL, respectively), ca. 20 mL fractions] gave 28j as a clear,

colorless oil (1.69 g, 98%, >99:1 dr). An analytically pure sample was obtained by further

purification of 28j (219 mg) via flash column chromatography [27 g SiO2, 24 mm Ø, wet loaded

with hexane, 98:2 hexane/EtOAc (400 mL), ca. 10 mL fractions], followed by Kugelrohr

distillation at reduced pressure (0.05 mm Hg), to give 28j as a clear, colorless oil (214 mg, 98%

mass return).

Data for 28j: bp: 158 °C (ABT) (0.05 mm Hg)


δ 7.31–7.25 (m, 2 H, HC(2′)), 7.21–7.16 (m, 3 H, HC(3′,4′)), 5.51–5.42 (m, 2 H,

HC(4,5)), 3.67 (t, J = 6.5 Hz, 2 H, HC(1)), 2.70–2.63 (m, 2 H, HC(7)), 2.34–2.27

(m, 2 H, HC(6)), 2.06 (q, J = 7.0, 6.3 Hz, 2 H, HC(3)), 1.59 (app pent, J = 6.6 Hz, 2

H, HC(2)), 1.13–1.02 (m, 21 H, Sii-Pr3) 13C NMR: (126 MHz, CDCl3)

δ 142.2 (C(1′)), 130.6 & 129.6 (C(4,5)), 128.4 (C(2′)), 128.2 (C(3′)), 125.7 (C(4′)),

62.8 (C(1)), 36.1 (C(7)), 34.5 (C(6)), 32.8 (C(2)), 28.8 (C(3)), 18.0 (SiCH(CH3)2),

12.0 (SiCH(CH3)2)

IR: (neat)

3086 (w), 3063 (w), 3028 (w), 2941 (s), 2893 (m), 2865 (s), 2726 (w), 1605 (w),

1497 (w), 1463 (m), 1455 (w), 1383 (w), 1366 (w), 1247 (w), 1108 (m), 1070 (w),

1031 (w), 1013 (w), 996 (w), 967 (m), 919 (w), 883 (w), 785 (w), 744 (w), 698 (m),

681 (m), 659 (w)

MS: (ESI+, TOF)

403.4 (14), 390.4 (32), 389.3 (75), 347.3 ([M+H]+, 4), 231.2 (11), 230.2 (34), 229.2

(100), 215.2 (21), 175.2 (12), 174.2 (29), 173.3 (53), 173.1 (91), 157.2 (21), 131.1

(17)

HRMS: (ESI+, TOF)





TLC: Rf 0.56 (99:1 hexane/MTBE) [UV/KMnO4]

Analysis: C22H38OSi (346.63)

Calcd: C, 76.23; H, 11.05%

Found: C, 76.38; H, 11.22%

Preparation of (E)-Hex-4-en-1-yl cyclopropanecarboxylate (28l)


charged with 4-N,N-dimethylaminopyridine (74 mg, 0.61 mmol, 10 mol %) then was sealed with

a rubber septum and purged with argon via an inlet needle. Et2O (6 mL), cyclopropanecarboxylic

acid (519 mg, 0.48 mL, 6.03 mmol, 1.0 equiv), and (E)-4-hexen-1-ol (639 mg, 0.75 mL, 6.37

mmol, 1.05 equiv) were sequentially added via syringe. The mixture was then cooled in an ice-

water bath and stirring was commenced. N,N′-Dicyclohexylcarbodiimide (1.36 g, 6.60 mmol, 1.1

equiv) was added in one portion against a backflow of argon and the resultant mixture was

stirred in the ice-water bath and allowed to gradually warm to rt over 18 h to give a thick, white

slurry. The reaction mixture was filtered through a pad of Celite (10 g, 35 mm) under house

vacuum to remove the urea by-product, which was rinsed with Et2O (50 mL). The filtrate was

concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil. Caution: the product

is volatile and should not be left on the rotary evaporator for an extended period. Purification

via flash column chromatography [90 g SiO2, 42 mm Ø, wet loaded with hexane, 96:4

hexane/EtOAc (1 L), ca. 20 mL fractions] gave a clear, pale yellow oil (1.03 g). Further

purification via Kugelrohr distillation at reduced pressure (10 mm Hg) gave 28l as a clear,

colorless oil (994 mg, 98%, >99:1 dr).

Data for 28l: bp: 81 °C (ABT) (10 mm Hg)


δ 5.49–5.36 (m, 2 H, HC(4,5)), 4.06 (t, J = 6.7 Hz, 2 H, HC(1)), 2.05 (dt, J = 7.5,

6.7 Hz, 2 H, HC(3)), 1.71–1.62 (m, 5 H, HC(2,6)), 1.59 (ddd, J = 12.7, 8.1, 4.6 Hz,




1 H, HC(8)), 1.00–0.96 (m, 2 H, HC(9,10)), 0.86–0.81 (m, 2 H, HC(9,10)) 13C NMR: (126 MHz, CDCl3)

δ 174.9 (C(7)), 130.0 & 125.8 (C(4,5)), 64.0 (C(1)), 28.8 (C(3)), 28.5 (C(2)), 17.9

(C(6)), 12.9 (C(8)), 8.3 (C(9,10))

IR: (neat)

3387 (w), 3021 (w), 2938 (w), 2853 (w), 1729 (m), 1451 (w), 1403 (w), 1372 (w),

1266 (w), 1172 (m), 1135 (s), 1106 (m), 996 (w), 967 (w), 914 (w), 615 (m)

MS: (CI+, DFSF)

169.1 ([M+H]+, 2), 135.0 (11), 83.1 (39), 82.1 (26), 69.0 (22), 67.0 (16), 65.0 (32),

63.0 (100), 62.0 (25), 61.0 (13), 59.0 (57)

HRMS: (EI+, DFSF)


TLC: Rf 0.45 (96:4 hexane/EtOAc) [KMnO4]

Preparation of (E)-2-Benzyl-2-(pent-3-en-1-yl)-1,3-dioxolane (28m)

Preparation of (E)-4-hexenoic acid (S1). An oven-dried, 50-mL, round-bottomed flask

equipped with a magnetic stirrer bar was charged sequentially with ethyl (E)-4-hexenoate (28k)

(1.42 g, 10.0 mmol, 1.0 equiv), EtOH (6.0 mL), H2O (6.0 mL), and NaOH (2.31 g, 57.8 mmol,

5.8 equiv) then was fitted with a water-jacketed condenser (sealed with a rubber septum at the

top) and purged with argon via an inlet needle. Stirring was commenced and the reaction mixture

was refluxed at 98–100 °C (oil bath temperature) for 3 h, then was allowed to cool to rt. The

reaction mixture was diluted with H2O (20 mL) and transferred to a separatory funnel, then

extracted with Et2O (3 × 10 mL). The combined organic extracts were discarded and the aqueous




layer was then cooled in an ice-water bath, acidified with 2 M HCl to pH 2 (with stirring),

transferred to a separatory funnel, and extracted with CH2Cl2 (3 × 20 mL). The combined

organic extracts were washed with H2O (20 mL) and brine (20 mL), then dried (MgSO4),

filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a colorless oil. Purification

via Kugelrohr distillation at reduced pressure (10 mm Hg) gave S1 as a clear, colorless oil (1.12

g, 98%, >99:1 dr). The 1H NMR spectroscopic data matched that reported in the literature.16

Data for S1:

bp: 145 °C (ABT) (10 mm Hg)


δ 11.86 (br s, 1 H, COOH), 5.54–5.39 (m, 2 H, HC(4,5)), 2.41 (ddd, J = 7.9, 7.1,

1.0 Hz, 2 H, HC(2)), 2.34–2.25 (m, 2 H, HC(3)), 1.64 (dq, J = 6.3, 1.3 Hz, 3 H,

HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 180.0 (C(1)), 128.8 (C(4)), 126.4 (C(5)), 34.1 (C(2)), 27.5 (C(3)), 17.8 (C(6))

Preparation of (E)-N-Methoxy-N-methylhex-4-enamide (S2). A flame-dried, 50-mL,

round-bottomed flask equipped with a magnetic stirrer bar was charged with (E)-4-hexenoic acid

(S10) (572 mg, 5.01 mmol, 1.0 equiv) then was sealed with a rubber septum and purged with

argon via an inlet needle. CH2Cl2 (14 mL) was added and stirring was commenced. The mixture

was cooled in an ice-water bath and 1,1′-carbonyldiimidazole (977 mg, 6.02 mmol, 1.2 equiv)

was added in one portion against a backflow of argon, and the resultant mixture was stirred in the

ice-water bath for 30 min. N,O-Dimethylhydroxylamine hydrochloride (1.22 g, 12.5 mmol, 2.5

equiv) was then added in one portion against a backflow of argon. The reaction flask was

removed from the ice-water bath and the resultant mixture was allowed to warm to rt over 7 h.

The reaction mixture was then filtered through a sintered funnel under house vacuum to remove

the amine salt, which was rinsed with CH2Cl2 (50 mL). The filtrate was transferred to a

separatory funnel and the organic layer was washed sequentially with 2 M HCl (30 mL), 2 M

NaOH (30 mL), and brine (30 mL), then dried (MgSO4), filtered, and concentrated in vacuo (20–

23 °C, ca. 20 mm Hg) to give a colorless oil. Purification via Kugelrohr distillation at reduced

pressure (130 °C, 5 mm Hg) gave S2 as a clear, colorless oil (782 mg, 99%, >99:1 dr). The 1H

and 13C NMR spectroscopic data matched that for alternative preparations.17




Data for S2:

bp: 130 °C (ABT) (5 mm Hg)


δ 5.52–5.37 (m, 2 H, HC(4,5)), 3.65 (s, 3 H, N(Me)OMe), 3.15 (s, 3 H,

N(Me)OMe), 2.45 (t, J = 7.4 Hz, 2 H, HC(4)), 2.34–2.19 (m, 2 H, HC(3)), 1.66–

1.55 (m, 3 H, HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 174.0 (C(1)), 129.8 (C(4)), 125.6 (C(5)), 61.1 (N(Me)OMe), 32.0 (N(Me)OMe)),

31.8 (C(2)), 27.4 (C(3)), 17.9 (C(6))

Preparation of (E)-1-Phenylhept-5-en-2-one (S3). A flame-dried, 50-mL, round-

bottomed flask equipped with a magnetic stirrer bar was charged with (E)-N-methoxy-N-

methylhex-4-enamide (S2) (629 mg, 4.00 mmol, 1.0 equiv) then was sealed with a rubber septum

and purged with argon via an inlet needle. THF (14 mL) was added and stirring was commenced.

The mixture was cooled in an ice-water bath (bath temperature ca. 0 °C) and benzylmagnesium

chloride (2.0 M in THF, 4.2 mL, 8.40 mmol, 2.1 equiv) was slowly added via syringe under an

argon atmosphere over 5 min. The resultant yellow-brown mixture was allowed to stir in the ice-

water bath and gradually warm to rt over 20 h, then was re-cooled in an ice-water bath and

carefully quenched with 2 M HCl (20 mL). The mixture was transferred to a separatory funnel

and the aqueous layer was extracted with Et2O (3 × 20 mL). The combined organic extracts were

washed with brine (20 mL) then dried (MgSO4), filtered, and concentrated in vacuo (20–23 °C,

ca. 20 mm Hg) to give a yellow oil. Purification via flash column chromatography [37 g SiO2, 30

mm Ø, dry loaded with 2 g SiO2, 100:0 → 98:2 → 95:5 hexane/Et2O (200 mL, 300 mL, and 300

mL, respectively), ca. 10 mL fractions], followed by further purification via flash column

chromatography under the same conditions, gave S3 as a clear, pale yellow oil (455 mg, 60%,

>99:1 dr). Caution: the product is volatile at ca. 0.05 mm Hg – some material was lost as a

result.

Data for S3:


δ 7.35–7.31, 7.29–7.24 & 7.22–7.18 (m, 5 H, HC(2′,3′,4′)), 5.45–5.31 (m, 2 H,

HC(5,6)), 3.68 (s, 2 H), 2.50 (t, J = 7.4 Hz, 2 H, HC(3)), 2.26–2.20 (m, 2 H, HC(4)),




1.61 (dd, J = 6.0, 1.2 Hz, 3 H, HC(7)) 13C NMR: (126 MHz, CDCl3)

δ 207.8 (C(2)), 134.2 (C(1′)), 129.38 (C(2′)), 129.37 (C(5)), 128.7 (C(3′)), 126.9

(C(4′)), 125.9 (C(6)), 50.2 (C(1)), 41.8 (C(3)), 26.7 (C(4)), 17.8 (C(7))

IR: (neat)

3063 (w), 3028 (m), 2959 (w), 2918 (m), 2855 (w), 1714 (s), 1603 (w), 1585 (w),

1496 (m), 1454 (m), 1408 (w), 1361 (w), 1315 (w), 1189 (w), 1113 (w), 1075 (w),

1031 (w), 967 (m), 732 (w), 699 (m)

MS: (ESI+, TOF)

217.1 (12), 216.1 (34), 211.1 ([M+Na]+, 29), 208.1 (85), 206.2 (12), 190.1 (14),

189.1 ([M+H]+, 100), 143.6 (19), 134.6 (21), 119.1 (15), 91.1 ([CH2Ph]+, 45)

HRMS: (ESI+, TOF)

calcd for C13H17O ([M+H]+): 189.1279, found: 189.1285

TLC: Rf 0.28 (96:4 hexane/EtOAc) [UV/KMnO4]

Preparation of (E)-2-Benzyl-2-(pent-3-en-1-yl)-1,3-dioxolane (28m). A flame-dried,

50-mL, round-bottomed flask equipped with a magnetic stirrer bar was charged with (E)-1-

phenylhept-5-en-2-one (S3) (390 mg, 2.07 mmol, 1.0 equiv) and p-toluenesulfonic acid

monohydrate (8.2 mg, 0.04 mmol, 2 mol %) then was sealed with a rubber septum and purged

with argon via an inlet needle. Toluene (20 mL) and ethylene glycol (1.11 g, 1.0 mL, 17.9 mmol,

8.6 equiv) were added sequentially, then the rubber septum was replaced with a Dean-Stark trap

fitted with a condenser (sealed at the top with a rubber septum), and the apparatus was purged

with argon via an inlet needle. The resultant mixture was refluxed at 148–149 °C (oil bath

temperature) for 24 h (N.B. ca. 0.9 mL H2O was collected in the receiver of the Dean-Stark trap

at the end of the reaction). The reaction mixture was then allowed to cool to rt and was

transferred to a separatory funnel and diluted with Et2O (20 mL). The organic phase was washed

sequentially with sat. aq. NaHCO3 (2 × 10 mL) and brine (10 mL), then dried (MgSO4), filtered,

and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil. Purification via

flash column chromatography [26 g SiO2, 24 mm Ø, dry loaded with 1.9 g SiO2, 97:3

hexane/EtOAc (400 mL), ca. 10 mL fractions)], followed by further purification via flash column




chromatography under the same conditions, gave 28m as a clear, colourless oil (461 mg, 96%,

>99:1 dr). An analytically pure sample was obtained by further purification of 28m (216 mg) via

Kugelrohr distillation at reduced pressure (0.05 mm Hg) to give 28m as a clear, colourless oil

(211 mg, 98% mass return).

Data for 28m: bp: 100 °C (ABT) (0.05 mm Hg)


δ 7.30–7.25 & 7.25–7.20 (m, 5 H, HC(2′,3′,4′)), 5.47–5.35 (m, 2 H, HC(5,6)), 3.90–

3.83 (m, 2 H, HC(8,9)), 3.73–3.66 (m, 2 H, HC(8,9)), 2.89 (s, 2 H, HC(1)), 2.14–

2.06 (m, 2 H, HC(4)), 1.69–1.64 (m, 2 H, HC(3)), 1.64–1.61 (m, 3 H, HC(7)) 13C NMR: (126 MHz, CDCl3)

δ 136.8 (C(1′)), 130.9 (C(5)), 130.5 (C(2′)), 127.9 (C(3′)), 126.3 (C(4′)), 124.8

(C(6)), 111.1 (C(2)), 65.3 (C(8,9)), 43.9 (C(1)), 37.8 (C(3)), 26.6 (C(4)), 17.9

(C(7))

IR: (neat)

3086 (w), 3063 (w), 3029 (m), 2953 (m), 2922 (m), 2884 (m), 2856 (m), 1605 (w),

1496 (m), 1475 (m), 1454 (w), 1377 (w), 1324 (w), 1258 (w), 1198 (m), 1124 (m),

1077 (m), 1048 (m), 967 (m), 950 (m), 851 (w), 751 (m), 700 (m), 671 (w), 640 (w),

617 (w)

MS: (ESI+, TOF)

284.3 (34), 282.3 (24), 256.3 (26), 249.2 (13), 233.2 ([M+H]+, 35), 231.2 (11),

190.1 (13), 189.1 ([M–(CH2CH2O)+H]+, 84), 187.1 (18), 171.1 (32), 163.1 ([M–

(CH3CH=CHCH2CH2)]+, 59), 141.1 ([M–(CH2Ph)]+, 20), 129.1 (20), 124.1 (24),

119.1 (30), 99.1 (12), 91.1 ([CH2Ph]+, 100)

HRMS: (ESI+, TOF)



Analysis: C15H20O2 (232.32)

Calcd: C, 77.55; H, 8.68%

Found: C, 77.97; H, 8.67%




Preparation of Methyl (2E,6E)-Octa-2,6-dienoate (28n)

A flame-dried, 100-mL, round-bottomed flask equipped with a magnetic stirrer bar and

rubber septum was purged with argon via an inlet needle then was charged sequentially with

CH2Cl2 (25 mL) and oxalyl chloride (1.14 g, 0.76 mL, 8.98 mmol, 1.5 equiv) via syringe, and

stirring was commenced. The solution was cooled at –78 °C in a dry ice-acetone bath under an

argon atmosphere, then anhydrous DMSO (1.43 g, 1.3 mL, 18.3 mmol, 3.0 equiv) was added

dropwise via syringe over 5 min, and the resultant mixture was allowed to stir at –78 °C for a

further 5 min. (E)-4-Hexen-1-ol (604 mg, 0.71 mL, 6.03 mmol, 1.0 equiv) was then added via

cannula transfer over 10 min using two portions of CH2Cl2 (4 mL and 2 mL), and the resultant

white suspension was stirred at –78 °C for 30 min. Triethylamine (3.66 g, 5.0 mL, 36.1 mmol,

6.0 equiv) was then added via syringe and the mixture was allowed to warm to –5 °C with

stirring over 2 h, then the dry ice-acetone bath was replaced with an ice-water bath. A solution of

methyl(triphenylphosphoranylidene)acetate (4.02 g, 12.0 mmol, 2.0 equiv) in CH2Cl2 (10 mL)

was then transferred into the reaction mixture via cannula, and the resultant mixture was allowed

to stir in the ice-water bath and gradually warm to rt over 20 h. The mixture was then transferred

to a separatory funnel containing H2O (50 mL) and the aqueous layer was extracted with Et2O (3

× 30 mL). The combined organic layers were washed with brine (30 mL), then dried (MgSO4),

filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a thick, yellow paste (95:5

E/Z). Caution: the product is volatile and should not be left on the rotary evaporator for an

extended period. Purification via flash column chromatography [66 g SiO2, 34 mm Ø, dry

loaded, 99:1 hexane/Et2O (1.2 L), ca. 20 mL fractions then 28 g SiO2, 24 mm Ø, wet loaded,

100:0 → 99:1 hexane/EtOAc (100 mL and 500 mL, respectively), ca. 10 mL fractions] gave a

colourless oil (785 mg). Further purification via Kugelrohr distillation at reduced pressure (5 mm

Hg) gave 28n as a clear, colourless oil (772 mg, 83%, >99:1 dr).

Data for 28n: bp: 81 °C (ABT) (5 mm Hg)





δ 6.96 (dt, J = 15.7, 6.8 Hz, 1 H, HC(3)), 5.82 (dt, J = 15.7, 1.6 Hz, 1 H, HC(2)),

5.50–5.36 (m, 2 H, HC(6,7)), 3.72 (s, 3 H, CO2Me), 2.25 (q, J = 7.5 Hz, 2 H,

HC(4)), 2.13 (q, J = 6.7 Hz, 2 H, HC(5)), 1.64 (dt, J = 6.2, 1.3 Hz, 3 H, HC(8)) 13C NMR: (126 MHz, CDCl3)

δ 167.1 (C(1)), 149.0 (C(3)), 129.5 (C(6)), 126.1 (C(7)), 121.0 (C(2)), 51.4

(CO2Me), 32.2 (C(4)), 31.0 (C(5)), 17.9 (C(8))

IR: (neat)

3027 (w), 2993 (w), 2950 (m), 2855 (w), 1727 (s), 1659 (m), 1436 (m), 1378 (w),

1324 (w), 1271 (m), 1203 (m), 1164 (m), 1126 (w), 1041 (m), 967 (m), 852 (w),

718 (w)

MS: (EI+, DFSF)

154.1 (M+, 13), 123.1 ([M–OMe]+, 50), 122.1 (28), 100.0 (100), 95.1 ([M–

CO2Me]+, 46), 94.1 (25), 69.0 ([CH3CH=CHCH2CH2]+, 60), 68.0 (54), 67.0 (23),

55.1 ([CH3CH=CHCH2]+, 100), 53.1 (29)

HRMS: (EI+, DFSF)

calcd for C9H14O2 (M+): 154.09938, found: 154.09916


Preparation of tert-Butyl (Z)-benzyl(hex-4-en-1-yl)carbamate (28o)

Preparation of tert-Butyl Benzylcarbamate (S5). A flame-dried, 50-mL, round-

bottomed flask equipped with a magnetic stirrer bar and rubber septum was purged with argon

via an inlet needle, then was charged sequentially with CH2Cl2 (15 mL), benzylamine (647 mg,

660 µL, 6.04 mmol, 1.0 equiv), and triethylamine (944 mg, 1.3 mL, 9.33 mmol, 1.5 equiv) via

syringe, and stirring was commenced. The resultant mixture was cooled in an ice-water bath then




di-tert-butyl dicarbonate (1.61 g, 1.7 mL, 7.40 mmol, 1.2 equiv) was added via syringe over 2–3

min, and the resultant mixture was allowed to warm to rt over 4 h. The reaction mixture was then

transferred to a separatory funnel, diluted with CH2Cl2 (30 mL), and washed sequentially with

H2O (2 × 20 mL) and brine (20 mL), then dried (MgSO4), filtered, and concentrated in vacuo

(20–23 °C, ca. 20 mm Hg) to give a colourless, viscous oil. Purification via flash column

chromatography [75 g SiO2, 42 mm Ø, dry loaded, 92:8 hexane/EtOAc (1.2 L), ca. 20 mL

fractions] gave S5 as a clear, colourless, viscous oil, which solidified to a white solid on standing

in a –20 °C freezer for ca. 1 day (1.25 g, quant.). The 1H and 13C NMR spectroscopic data

matched that for alternative preparations.18

Data for S5:


δ 7.34–7.22 (m, 5 H, HC(2′,3′,4′)), 4.98 (br s, 1 H, NH), 4.30 (d, J = 5.4 Hz, 2 H,

HC(5’)), 1.46 (s, 9 H, Ot-Bu) 13C NMR: (126 MHz, CDCl3)

δ 155.8 (NCO2CMe3), 138.9 (C(1′)), 128.5 (C(3′)), 127.4 (C(4′)), 127.2 (C(2′)),

79.3 (NCO2CMe3), 44.5 (C(5’)), 28.3 (NCO2CMe3)

Preparation of tert-Butyl (Z)-Benzyl(hex-4-en-1-yl)carbamate (28o). An oven-dried,

25-mL, Schlenk flask equipped with a magnetic stirrer bar was charged with NaH (washed, 108

mg, 4.50 mmol, 1.5 equiv) in the glovebox, and was then sealed with a rubber septum and

removed from the box. DMF (7.5 mL) was then added via syringe under an atmosphere of argon

and stirring was commenced. The suspension was cooled in an ice-water bath then tert-butyl

benzylcarbamate S5 (622 mg, 3.00 mmol, 1.0 equiv) was added via cannula transfer using two

portions of DMF (2 × 2.0 mL), and the resultant mixture was stirred in the ice-water bath for 10

min, then was allowed to warm to rt over 30 min at rt (N.B. generation of H2 gas was only

observed when the temperature was elevated). (Z)-6-Iodo-2-hexene (662 mg, 3.15 mmol, 1.05

equiv) was added via syringe using two portions of DMF (2 × 1.0 mL), then the rubber septum

was replaced with a water-jacketed reflux condenser (sealed at the top with a rubber septum).

The mixture was allowed to stir at rt for 30 min then was heated at 70–72 °C (oil bath

temperature) for a further 18 h. Once the reaction had been allowed to cool to rt, it was carefully

quenched with H2O (2 mL), transferred to a separatory funnel, and diluted with H2O (20 mL).




The aqueous layer was extracted with Et2O (3 × 20 mL) and the combined organic extracts were

washed sequentially with H2O (20 mL) and brine (20 mL), then dried (MgSO4), filtered, and

concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil. Purification via flash

column chromatography [88 g SiO2, 42 mm Ø, dry loaded, 97:3 hexane/EtOAc (1 L), ca. 20 mL

fractions] gave 28o as a clear, colourless oil (718 mg, 83%, >99:1 dr). An analytically pure

sample was obtained by further purification of 28o (279 mg) via flash column chromatography

[28 g SiO2, 24 mm Ø, wet loaded with CH2Cl2, 97:3 hexane/EtOAc (400 mL), ca. 10 mL

fractions] followed by Kugelrohr distillation at reduced pressure (0.05 mm Hg) to give 28o as a

clear, colorless oil (275 mg, >99:1 dr, 99% mass return).

Data for 28o: bp: 158 °C (ABT) (0.05 mm Hg)

1H NMR: (500 MHz, MeCN-d3, VT at 53 °C, calibrated with ethylene glycol)

δ 7.36–7.31 (m, 2 H, HC(2′)), 7.29–7.24 (m, 3 H, HC(3′,4′)), 5.49–5.33 (m, 2 H,

HC(4,5)), 4.42 (s, 2 H, HC(5′)), 3.19 (t, J = 7.4 Hz, 2 H, HC(1)), 2.00 (q, J = 7.3 Hz,

2 H, HC(3)), 1.59–1.51 (m, 5 H, HC(2,6)), 1.45 (s, 3 H, Ot-Bu) 13C NMR: (126 MHz, MeCN-d3, VT at 53 °C, calibrated with ethylene glycol)

[N.B. partial isomerization (ca. 1%) of the (Z)-olefin was observed after heating at

53 °C for 1 h whilst collecting the 13C NMR spectroscopic data]

δ 156.7 (NCO2CMe3), 140.4 (C(1′)), 131.0 (C(4)), 129.5 (C(3′)), 128.5 (C(4′)),

128.1 (C(2′)), 125.2 (C(5)), 80.1 (NCO2CMe3), 51.4 (C(5′)), 47.7 (C(1)), 29.1 &

29.0 (C(2), NCO2CMe3), 25.1 (C(3)), 13.1 (C(6))

IR: (neat)

3011 (w), 2975 (m), 2931 (m), 1696 (s), 1605 (w), 1496 (w), 1453 (m), 1415 (m),

1391 (w), 1365 (m), 1241 (m), 1165 (m), 1134 (m), 1029 (w), 987 (w), 878 (w),

770 (w), 733 (w), 699 (m)

MS: (ESI+, TOF)

312.2 ([M+Na]+, 28), 291.2 (12), 290.2 ([M+H]+, 57), 235.2 (20), 234.2 (100),

164.1 (40), 91.1 ([CH2Ph]+, 30)

HRMS: (ESI+, TOF)

calcd for C18H28NO2 ([M+H]+): 290.2120, found: 290.2119





Analysis: C18H27NO2 (289.42)

Calcd: C, 74.70; H, 9.40; N, 4.84%

Found: C, 74.92; H, 9.44; N, 5.11%

Preparation of (Z)-2-(Hex-4-en-1-yl)isoindoline-1,3-dione (28p)

A flame-dried, 25-mL, Schlenk flask equipped with a magnetic stirrer bar and water-

jacketed reflux condenser was charged with (Z)-6-iodo-2-hexene (630 mg, 3.00 mmol, 1.0 equiv)

and DMF (15 mL) under an argon atmosphere, then stirring was commenced. Potassium

phthalimide (680 mg, 3.60 mmol, 1.2 equiv) was added against a backflow of argon and the

resultant mixture was heated at 90 °C for 14.5 h. The reaction mixture was then allowed to cool

to rt and was transferred to a separatory funnel, then diluted with H2O (75 mL) and EtOAc (50

mL). The layers were separated and the aqueous layer was extracted with EtOAc (2 × 50 mL).

The combined organic extracts were then washed with H2O (5 × 50 mL), dried (MgSO4), filtered,

and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a yellow oil (730 mg). Purification

via flash column chromatography (40 g SiO2, 30 mm Ø, 90:10 hexanes/MTBE, ca. 5 mL

fractions) gave a colourless oil (684 mg). Further purification via Kugelrohr distillation at

reduced pressure (0.01 mm Hg) gave 28p as a clear, colorless oil, which solidified to a white

semi-solid on standing in a –20 °C freezer for ca. 1 day (650 mg, 94%, >99:1 dr, ca. 97% purity,

contaminated with a regioisomeric terminal alkene impurity and an unidentified hydrocarbon

impurity). The 1H NMR spectroscopic data matched that for alternative preparations.19

Data for 28p: bp: 120 °C (ABT) (0.01 mm Hg)


δ 7.87–7.81 (m, 2 H, HC(3′)), 7.74–7.68 (m, 2 H, HC(4′)), 5.52–5.34 (m, 2 H,

HC(4,5)), 3.69 (dd, J = 8.1, 6.8 Hz, 2 H, HC(1)), 2.11 (q, J = 7.4 Hz, 2 H, HC(3)),

1.80–1.70 (m, 2 H, HC(2)), 1.60 (ddd, J = 6.6, 1.5, 0.7 Hz, 3 H, HC(6))




13C NMR: (126 MHz, CDCl3)

δ 168.3 (C(1′)), 133.7 (C(4′)), 132.1 (C(2′)), 129.0 (C(4)), 124.8 (C(5)), 123.0

(C(3′)), 37.6 (C(1)), 28.2 (C(2)), 24.2 (C(3)), 12.7 (C(6))

Preparation of (E)-tert-Butyl(hex-2-en-1-yloxy)diphenylsilane (28q)


imidazole (309 mg, 4.50 mmol, 1.5 equiv) and trans-2-hexen-1-ol (313 mg, 371 µL, 3.00 mmol,




mixture was stirred under argon at rt for 16 h. The reaction mixture was then transferred to a

separatory funnel and diluted with CH2Cl2 (25-mL), washed sequentially with H2O (10 mL) and



wet loaded, 99:1 hexane/MTBE, ca. 5 mL fractions) gave 28q as a clear, colorless oil (900 mg,

89%, >99:1 dr, contaminated with ca. 4% regioisomeric alkene contaminants).

Data for 28q: 1H NMR: (500 MHz, CDCl3)

7.73–7.69 (m, 4 H, HC(2′,2′′)), 7.46–7.37 (m, 6 H, HC(3′,3′′,4′,4′′), 5.71–5.63 &

5.60–5.53 (m, 2 H, HC(2,3)), 4.23–4.14 (m, 2 H, HC(1)), 2.05–1.99 (m, 2 H,

HC(4)), 1.40 (sextet, J = 7.4 Hz, 2 H, HC(5)), 1.08 (s, 9 H, Sit-Bu), 0.92 (t, J = 7.4

Hz, 3 H, HC(6)). 13C NMR: (126 MHz, CDCl3)

135.5 (C(2′,2′′)), 133.9 (C(1′,1′′)), 131.2 (C(2)), 129.5 (C(4′,4′′)), 128.8 (C(3)),

127.6 (C(3′,3′′), 64.7 (C(1)), 34.3 (C(4)), 26.9 (SiCMe3), 22.4, (C(5)), 19.2

(SiCMe3), 13.7 (C(6))




IR: (neat)

3071 (w), 3051 (w), 2956 (m), 2931 (m), 2895 (w), 2858 (m), 1591 (w), 1473 (w),

1462 (w), 1428 (m), 1379 (w), 1362 (w), 1112 (s), 1058 (m), 1009 (w), 969 (m),

823 (m), 739 (m), 701 (s)

MS: (EI+, TOF)

338.2 (M+, 29), 337.2 (13), 336.2 (14), 323.2 ([M-CH3]+, 18), 296.1 (17), 295.1

([M-CH3CH2CH2]+, 69), 282.1 ([M-CH3CH2CH2CH]+, 22), 281.1 (98), 203.1 (29),

200.1 (17), 199.1 (100), 197.1 (13), 183.0 (13), 181.0 (16)


HRMS: (EI+, TOF)

calcd for C22H30OSi (M+): 338.2066, found: 338.2058

Preparation of (E)-tert-Butyldimethyl[(5-phenylpent-2-en-1-yl)oxy]silane (28s)


(E)-5-phenylpent-2-en-1-ol 28u (487 mg, 3.00 mmol, 1.0 equiv) and imidazole (309 mg, 4.50

mmol, 1.5 equiv) then was sealed with a rubber septum and purged with argon via an inlet

needle. CH2Cl2 (6 mL) was then added and stirring was commenced. tert-Butyldimethylsilyl

chloride (497 mg, 3.30 mmol, 1.1 equiv) was added in one portion against a backflow of argon

and the resultant mixture was stirred at rt for 22 h. The reaction mixture was then transferred to a

separatory funnel and diluted with CH2Cl2 (25 mL), then was washed sequentially with H2O (10

mL) and brine (10 mL), then dried (MgSO4), filtered, and concentrated in vacuo (45 °C, ca. 5

mm Hg) to give a colorless oil (886 mg). Purification via flash column chromatography (40 g

SiO2, 30 mm Ø, wet loaded, 98:2 hexane/MTBE, ca. 5 mL fractions) gave a colorless oil (785

mg). Further purification via Kugelrohr distillation at reduced pressure (10–5 mm Hg) gave 28s

as a clear, colorless oil (758 mg, 91%, >99:1 dr). The 1H and 13C NMR spectroscopic data

matched that for alternative preparations.20




Data for 28s: bp: 100 °C (ABT) (10–5 mm Hg)


δ 7.32–7.27 (m, 2 H, HC(2′)), 7.24–7.17 (m, 3 H, HC(3′,4′)), 5.71 (dt, J = 15.4, 6.5

Hz, 1 H, HC(2)), 5.64–5.56 (m, 1 H, HC(3)), 4.14 (d, J = 5.2 Hz, 1 H, HC(1)), 2.71

(t, J = 7.9 Hz, 2 H, HC(5)), 2.41–2.34 (m, 2 H, HC(4)), 0.93 (s, 9 H, Sit-Bu), 0.08 (s,

6 H, SiMe2) 13C NMR: (126 MHz, CDCl3)

δ 141.9 (C(1′)), 130.2 (C(2)), 129.8 (C(2′)), 128.4 & 128.2 (C(3,3′)), 125.7 (C(4′)),

63.9 (C(1)), 35.6 (C(5)), 34.0 (C(4)), 26.0 (SiCMe3), 18.4 (SiCMe3), –5.1 (SiMe2)

Preparation of (E)-4-(Benzyloxy)but-2-en-1-ol (28w)

Preparation of 4-(benzyloxy)but-2-yn-1-ol (S6). Following a literature procedure,20 an

oven-dried, 100-mL, round-bottomed flask equipped with a magnetic stirrer bar was charged

with 2-butyne-1,4-diol (3.47 g, 40.3 mmol, 4.0 equiv) and an aqueous solution (30 mL) of KOH

(2.26 g, 40.3 mmol, 4.0 equiv), then was sealed with a glass stopper and stirred at rt for 5 min.

Benzyl bromide (1.72 g, 1.2 mL, 10.0 mmol, 1.0 equiv) was added dropwise via syringe over 2–

3 min and the resultant mixture was allowed to stir at rt for 48 h. The reaction mixture was then

transferred to a separatory funnel and extracted with CH2Cl2 (3 × 30 mL), and the combined

organic extracts were washed with brine (20 mL), then dried (MgSO4), filtered, and concentrated

in vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil. Purification via flash column

chromatography [40 g SiO2, 30 mm Ø, dry loaded, 95:5 → 90:10 → 80:20 → 70:30

hexane/EtOAc (100 mL, 100 mL, 300 mL, and 300 mL, respectively), ca. 20 mL fractions] gave

S6 as a colorless oil (1.56 g, 89%). The 1H NMR spectroscopic data matched that reported in the

literature.21




Data for S6:


δ 7.38–7.28 (m, 5 H, HC(2′,3′,4′)), 4.60 (s, 2 H, HC(5′)), 4.32 (s, 2 H, HC(4)), 4.22

(t, J = 1.8 Hz, 2 H, HC(1)), 1.71 (br s, 1 H, OH) 13C NMR: (100 MHz, CDCl3)

δ 137.0 (C(1′)), 128.3 (C(3′)), 128.0 (C(2′)), 127.8 (C(4′)), 84.9 (C(3)), 81.1 (C(2)),

71.5 (C(5′)), 57.2 (C(4)), 50.6 (C(1))

Preparation of (E)-4-(benzyloxy)but-2-en-1-ol (28w). A flame-dried, 25-mL, round-

bottomed flask equipped with a magnetic stirrer bar was charged with 4-(benzyloxy)but-2-yn-1-

ol S6 (250 mg, 1.42 mmol, 1.0 equiv) then was sealed with a rubber septum and purged with

argon via an inlet needle. THF (7 mL) was added and the mixture was cooled in an ice-water

bath with stirring under argon. Red-Al® (≥60 wt% in toluene) (570 mg, 550 µL, 1.69 mmol, 1.2

equiv) was then added dropwise via syringe (resulting in gas evolution) and the resultant mixture

was stirred in the ice-water bath for 3 h. The reaction mixture was quenched with MeOH (0.3

mL) at 0 °C and the resultant turbid mixture was acidified with 2 M HCl at rt to pH 2, then was

transferred to a separatory funnel, diluted with H2O (20 mL), and extracted with EtOAc (3 × 20

mL). The combined organic extracts were washed with brine (20 mL), dried (MgSO4), filtered,

and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil. Purification via

flash column chromatography [25 g SiO2, 24 mm Ø, dry loaded with 2 g SiO2, 90:10 → 80:20 →

65:35 hexane/EtOAc (100 mL, 200 mL, and 200 mL, respectively), ca. 10 mL fractions] gave

28w as a clear, pale yellow oil (204 mg, 81%). The 1H NMR spectroscopic data matched that for

alternative preparations.22

Data for 28w:


δ 7.45–7.26 (m, 5 H, HC(2′,3′,4′)), 5.97–5.81 (m, 2 H, HC(2,3)), 4.53 (s, 2 H,

HC(5′)), 4.20–4.15 (m, 2 H, HC(4)), 4.07–4.03 (m, 2 H, HC(1)), 1.50 (br s, 1 H,

OH) 13C NMR: (100 MHz, CDCl3)

δ 138.1 (C(1′)), 132.2 (C(3)), 128.4 (C(3′)), 127.8 & 127.7 (C(2′,4′)), 127.6 (C(2)),

72.3 & 70.0 (C(4,5’)), 63.0 (C(1))





Preparation of Bis(4-methoxyphenyl) Diselenide (26)

A flame-dried, 100-mL, three-necked, round-bottomed flask equipped with a magnetic

stirrer bar, glass stopper, rubber septum, and an argon inlet was charged with 4-bromoanisole

(514 mg, 370 µL, 3.00 mmol, 1.0 equiv) and THF (15 mL), and stirring was commenced. The

mixture was cooled in a dry ice-acetone bath at –78 °C and tert-butyllithium (1.6 M in pentane,

3.9 mL, 6.24 mmol, 2.1 equiv) was then added dropwise via syringe over 5 min (N.B. the

solution turned yellow at each drop and quickly decolorized; it then remained yellow more than

halfway into the addition). The resultant mixture was stirred at –78 °C for 15 min then the dry-

ice acetone bath was replaced with an ice-water bath, and the reaction was stirred for a further 45

min. Selenium powder (261 mg, 3.30 mmol, 1.1 equiv) was added in one portion against a

backflow of argon, and the resultant mixture was allowed to stir in the ice-water bath for 15 min,

followed by a further 45 min at rt, to give a red-brown solution. The reaction mixture was

quenched with 1 M HCl (2 mL), then was transferred to a separatory funnel, diluted with H2O

(20 mL), and extracted with Et2O (3 × 20 mL). The combined organic extracts were washed with

brine (20 mL), dried (MgSO4), filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to

give an orange-brown oil (caution: stench!). The oil was dissolved in EtOH (10 mL), charged

with a NaOH pellet (ca. 60 mg), and the resultant mixture was vigorously stirred under

atmospheric air at rt for 2 h to give a deep orange solution. The solvent was then removed in

vacuo (45 °C, ca. 20 mm Hg) to give an orange paste. Purification via flash column

chromatography [45 g SiO2, 30 mm Ø, dry loaded with 2.5 g SiO2, 96:4 hexane/EtOAc (800 mL),

ca. 20 mL fractions] gave 26 as a clear, orange oil, which solidified to an orange solid on

standing in a –20 °C freezer for ca. 1 day (528 mg, 95%). Further purification was performed via

recrystallization from boiling 98:2 hexane/Et2O (8 mL), with gradual cooling to rt over 22 h in a

20 mL scintillation vial loosely sealed with a screw top cap. The crystals were collected via

filtration through filter paper in a Hirsch funnel under house vacuum, washed with (–78 °C)

pentane (5 × ca. 1 mL), crushed with a spatula, and dried in vacuo (0.05 mm Hg) overnight to




give 26 as a yellow-orange, crystalline solid (458 mg, 87% mass return from the first crop). The 1H and 13C NMR spectroscopic data matched that for alternative preparations.23

Data for 26: mp: 51–53 °C (hexane/Et2O) [lit: 55–57 °C (MeOH)]24


δ 7.51 (d, J = 8.2 Hz, 4 H), 6.81 (d, J = 8.3 Hz, 4 H), 3.81 (s, 6 H) 13C NMR: (126 MHz, CDCl3)

δ 160.1, 135.45, 135.41, 135.36, 122.0, 114.7, 55.3

IR: (neat)

2931 (w), 2901 (w), 2834 (w), 1585 (m), 1570 (w), 1488 (s), 1460 (w), 1439 (w),

1287 (m), 1246 (s), 1171 (m), 1101 (w), 1070 (w), 1028 (m), 821 (m), 791 (w)

MS: (ESI+, TOF)

562.9 (17), 560.9 (40), 558.9 (49), 556.9 (37), 554.9 (21), 375.9 (12), 373.9 (M+,

36), 369.9 (19), 296.0 (20), 294.0 (100), 292.0 (52), 290.0 (18)

HRMS: (ESI+, TOF)

calcd for C14H14O2Se2 (M+): 373.9324, found: 373.9338


Preparation of Bis(2-methoxyphenyl) Diselenide (27)

A flame-dried, 100-mL, three-necked, round-bottomed flask equipped with a magnetic

stirrer bar, glass stopper, rubber septum, and an argon inlet was charged with 2-bromoanisole

(514 mg, 370 µL, 3.00 mmol, 1.0 equiv) and THF (15 mL), and stirring was commenced. The

mixture was cooled in a dry ice-acetone bath at –78 °C and tert-butyllithium (1.6 M in pentane,

3.9 mL, 6.24 mmol, 2.1 equiv) was then added dropwise via syringe over 5 min (N.B. the

solution turned yellow at each drop and quickly decolorized; it then remained yellow more than

halfway into the addition). The resultant mixture was stirred at –78 °C for 15 min then the dry-

ice acetone bath was replaced with an ice-water bath, and the reaction was stirred for a further 45




min. Selenium powder (262 mg, 3.32 mmol, 1.1 equiv) was added in one portion against a

backflow of argon, and the resultant mixture was allowed to stir in the ice-water bath for 15 min,

followed by a further 45 min at rt, to give a red-brown solution. The reaction mixture was

quenched with 1 M HCl (2 mL), then was transferred to a separatory funnel, diluted with H2O

(20 mL), and extracted with Et2O (3 × 20 mL). The combined organic extracts were washed with

brine (20 mL), dried (MgSO4), filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to

give an orange-brown oil (caution: stench!). The oil was dissolved in EtOH (10 mL), charged

with a NaOH pellet (ca. 60 mg), and the resultant mixture was vigorously stirred under

atmospheric air at rt for 2 h to give a deep orange solution. The solvent was then removed in

vacuo (45 °C, ca. 20 mm Hg) to give an orange paste. Purification via flash column

chromatography [48 g SiO2, 30 mm Ø, dry loaded with 2.5 g SiO2, 96:4 hexane/EtOAc (800 mL),

ca. 20 mL fractions], followed by further purification of the mixed fractions [40 g SiO2, 30 mm

Ø, dry loaded with 2.2 g SiO2, 96:4 hexane/EtOAc (800 mL), ca. 10 mL fractions], gave 27 as a

yellow solid (487 mg, 87%). Further purification of an aliquot (310 mg) of this material was

performed via recrystallization from boiling 90:10 hexane/CH2Cl2 (6 mL), with gradual cooling

to rt over 22 h in a 20 mL scintillation vial loosely sealed with a screw top cap. The crystals were

collected via filtration through filter paper in a Hirsch funnel under house vacuum, washed with

(–78 °C) hexane (5 × ca. 1 mL), crushed with a spatula, and dried in vacuo (0.05 mm Hg)

overnight to give 27 as a bright yellow, crystalline solid (283 mg, 91% mass return from the first

crop). The 1H NMR spectroscopic data matched that for alternative preparations.25

Data for 27: mp: 85–86 °C (hexane/CH2Cl2) [lit: 79 °C (EtOH)]25


δ 7.56 (dd, J = 7.7, 1.5 Hz, 2 H), 7.21 (ddd, J = 8.1, 7.5, 1.6 Hz, 2 H), 6.88 (td, J =

7.6, 1.1 Hz, 2 H), 6.84–6.79 (m, 2 H), 3.91 (s, 6H) 13C NMR: (126 MHz, CDCl3)

δ 156.8, 130.6, 128.1, 121.9, 118.6, 110.1, 55.9

IR: (neat)

3004 (w), 2937 (w), 2834 (w), 1573 (m), 1470 (s), 1447 (w), 1432 (m), 1303 (w),

1268 (m), 1237 (s), 1182 (w), 1159 (w), 1125 (w), 1053 (m), 1022 (m), 788 (w),

751 (s), 711 (w), 655 (w)




MS: (ESI+, TOF)

563.0 (34), 560.9 (85), 558.9 (100), 557.0 (79), 555.0 (45), 554.0 (18), 376.0 (13),

374.0 (M+, 41), 372.0 (37), 370.0 (21), 296.0 (11), 294.0 (54), 292.0 (27), 230.0

(18)

HRMS: (ESI+, TOF)

calcd for C14H14O2Se2 (M+): 373.9324, found: 373.9342



An oven-dried, 4-mL dram vial equipped with a magnetic stirrer bar was taken into the

glovebox and charged sequentially with diphenyl diselenide (PhSeSePh) (3.1 mg, 0.01 mmol, 5

mol %), the requisite tetraalkylammonium chloride (n-Bu4NCl or BnEt3NCl) (0.0–3.0 equiv),

and the requisite oxidant (N-fluoropyridinium tetrafluoroborate 11 or Selectfluor® 12) (0.26

mmol, 1.3 equiv), and was then sealed with a rubber septum, removed from the box, and placed

under argon via an inlet needle. MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL,

0.20 mmol, 1.0 equiv), and chlorotrimethylsilane (Me3SiCl) (0.0–3.0 equiv) were then added

sequentially via syringe, and stirring was commenced. After ca. 10 min, cyclohexene 6 (16.4 mg,

20.3 µL, 0.20 mmol, 1.0 equiv) was added via syringe, and the resultant suspension was stirred at

rt for ca. 20 h. The reaction mixture was then passed through a short plug of Celite (ca. 1 cm

depth in a Pasteur pipet) and the filtrate was analyzed by 1H NMR spectroscopy in order to

assess the product distribution and determine the syn/anti diastereoisomeric ratio (dr). NMR

yields were measured against 1,1,2,2-tetrachloroethane (1.0 equiv) as an internal standard using

diagnostic 1H NMR resonances measured for authentic samples of compounds 7–10 (and the

anti-diastereoisomer of 7) in MeCN-d3.

Data for 7: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.41–4.37 (m, 2 H, HC(1,2))

Data for the anti-diastereoisomer of 7: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.04–3.98 (m, 2 H, HC(1,2))




Data for 8: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only) δ 5.86–5.81 (m, 1 H, HC(3)), 5.76–5.72 (m, 1 H, HC(2))

Data for 9: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only) δ 4.18–4.10 (m, 1 H, HC(2)), 3.50–3.42 (m, 1 H, HC(1))

Data for 10: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only) δ 4.93 & 4.78 (ddd, J = 12.1, 10.7, 3.8 Hz, 1 H, ddd, J = 11.8, 10.8, 4.4 Hz, 1 H,

HC(1,2))

Reaction Development with Cyclohexene (Table 1)

Table 1 Entry 1

Following General Procedure I, PhSeSePh (3.1 mg, 0.01 mmol, 5 mol %), n-Bu4NCl

(167 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), MeCN-d3 (1.0 mL),

1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), and cyclohexene 6 (16.4 mg,

20 µL, 0.20 mmol, 1.0 equiv) were reacted to give: 6 (50%), 7 (19%, >99:1 dr), 8 (3%) and 9

(9%).




Table 1 Entry 2



1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (21.7 mg, 25.4 µL,

0.20 mmol, 1.0 equiv), and cyclohexene 6 (16.4 mg, 20 µL, 0.20 mmol, 1.0 equiv) were reacted

to give: 6 (12%), 7 (61%, >99:1 dr), 8 (10%), and 9 (10%).

Table 1 Entry 3





to give: 7 (81%, >99:1 dr) and 8 (10%).




Table 1 Entry 4





to give: 7 (81%, >99:1 dr) and 8 (8%).

Table 1 Entry 5





to give: 7 (74%, >99:1 dr) and 8 (10%).




Table 1 Entry 6

Following General Procedure I, PhSeSePh (3.1 mg, 0.01 mmol, 5 mol %), 11 (48.0 mg,

0.26 mmol, 1.3 equiv), MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20

mmol, 1.0 equiv), Me3SiCl (43.4 mg, 50.8 µL, 0.40 mmol, 2.0 equiv), and cyclohexene 6 (16.4

mg, 20 µL, 0.20 mmol, 1.0 equiv) were reacted to give: 6 (54%), 8 (2%), 10 (8%), and an

unidentified species (11%).

Table 1 Entry 7


(167 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), CD2Cl2 (1.0 mL), 1,1,2,2-

tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (43.4 mg, 50.8 µL, 0.40

mmol, 2.0 equiv), and cyclohexene 6 (16.4 mg, 20 µL, 0.20 mmol, 1.0 equiv) were reacted to

give: 7 (73%, >99:1 dr), 8 (12%) and 9 (4%).




Table 1 Entry 8


(167 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), THF-d8 (1.0 mL), 1,1,2,2-

tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (43.4 mg, 50.8 µL, 0.40

mmol, 2.0 equiv), and cyclohexene 6 (16.4 mg, 20 µL, 0.20 mmol, 1.0 equiv) were reacted to

give: 6 (55%), 7 (17%, >99:1 dr), and 8 (2%).

Table 1 Entry 9





to give: 7 (71%, >99:1 dr) and 8 (10%).

Table 1 Entry 10

Following General Procedure I, PhSeSePh (3.1 mg, 0.01 mmol, 5 mol %), BnEt3NCl







to give: 7 (83%, >99:1 dr) and 8 (10%).

Background Reaction (Omission of PhSeSePh)

Following General Procedure I (but with omission of PhSeSePh), BnEt3NCl (138 mg,

0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), MeCN-d3 (1.0 mL), 1,1,2,2-

tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (43.7 mg, 51 µL, 0.40 mmol,

2.0 equiv), and cyclohexene 6 (16.4 mg, 20 µL, 0.20 mmol, 1.0 equiv) were reacted to give: 6

(42%), anti-7 (~35%; diagnostic signal was overlapped with that from an unidentified species at

ca. δ 3.99–3.94), and 8 (16%).

General Procedure II: Survey of Lewis Base Additives with (E)-1-Benzyloxyl-4-hexene (17)

(Table 2, Entries 1-8)


glovebox and charged sequentially with diphenyl diselenide (PhSeSePh) (3.4 mg, 0.01 mmol, 5

mol %), benzyltriethylammonium chloride (BnEt3NCl) (138 mg, 0.60 mmol, 3.0 equiv), and N-

fluoropyridinium tetrafluoroborate 11 (48.0 mg, 0.26 mmol, 1.3 equiv). In the case of solid

Lewis base additives (entries 6 and 7), the requisite additive was also added at this point. The

vial was then sealed with a rubber septum, removed from the box, and placed under argon via an

inlet needle. MeCN-d3 (1.0 mL) and 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0

equiv) were then added sequentially via syringe. In the case of liquid Lewis base additives

(entries 3–5 and 8), the requisite additive was also added at this point via syringe. Finally,

chlorotrimethylsilane (Me3SiCl) (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv) was added via syringe




and stirring was commenced. After ca. 10 min, (E)-1-benzyloxyl-4-hexene 17 (38.1 mg, 39 µL,

0.20 mmol, 1.0 equiv) was added via syringe, then the argon inlet needle was removed and the

resultant suspension was stirred at rt. Once the reaction mixture had become homogeneous, it

was stirred for a further ca. 15 min and an aliquot (0.5 mL) was transferred via syringe into an

oven-dried NMR tube. The reaction mixture was then analyzed by 1H NMR spectroscopy in

order to assess the ratio of product 18 to by-products 19–22, and to determine the syn/anti

diastereoisomeric ratio (dr) for 18 (by comparison to an authentic sample of the anti-

diastereoisomer of 18). Relative ratios were determined using diagnostic 1H NMR resonances for

product 18 and by-products 19–22.

Data for 18: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.35 (qd, J = 6.6, 2.7 Hz, 1 H, HC(5)), 4.16 (ddd, J = 9.4, 4.1, 2.7 Hz, 1 H,

HC(4))

Data for the anti-diastereoisomer of 18: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)


HC(4))

Data for (19–22): 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 5.89 (ddd, J = 17.0, 10.2, 8.3 Hz, 1 H, HC(5) for 21), 5.78–5.71 & 5.68–5.62 (m,

2 H, HC(3,4) for 22), 5.69–5.62 (m, 1 H, HC(5) for 19), 5.57 (tq, J = 7.8, 1.2 Hz, 1

H, HC(4) for 20), 5.26 (dt, J = 16.9, 1.1 Hz, 1 H, HC(6) for 21), 5.12 (dt, J = 10.2,

0.9 Hz, 1 H, HC(6) for 21)




Survey of Lewis Base Additives (Table 2)

Table 2 Entry 1

Following General Procedure II, PhSeSePh (3.4 mg, 0.01 mmol, 5 mol %), BnEt3NCl


1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL,

0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted for 6

h to give complete conversion of 17 to a 80:20 mixture of 18 (99:1 dr):(19–22).

Table 2 Entry 2



sulfolane (0.25 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl

(44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv)

were reacted for 2 h to give complete conversion of 17 to a 80:20 mixture of 18 (99:1 dr):(19–

22).




Table 2 Entry 3



1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), hexamethylphosphoramide

(HMPA) (36.0 mg, 35 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0

equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted for 3 h to give

complete conversion of 17 to a 82:18 mixture of 18 (98:2 dr):(19–22).

Table 2 Entry 4



1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), N,N′-dimethylpropyleneurea

(DMPU) (25.4 mg, 24 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0

equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted for 3.5 h to give

complete conversion of 17 to a 80:20 mixture of 18 (98:2 dr):(19–22).




Table 2 Entry 5



1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), N,N′-dimethyl-2-

imidazolidinone (DMI) (23.2 mg, 22 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41

mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted for 2.5 h

to give complete conversion of 17 to a 80:20 mixture of 18 (99:1 dr):(19–22).

Table 2 Entry 6


(138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), triphenylphosphine oxide

(35.7 mg, 0.20 mmol, 1.0 equiv), MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL,

0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg,

39 µL, 0.20 mmol, 1.0 equiv) were reacted for 3.5 h to give complete conversion of 17 to a 80:20

mixture of 18 (98:2 dr):(19–22).




Table 2 Entry 7


(138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), pyridine N-oxide (19.0 mg,


mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39

µL, 0.20 mmol, 1.0 equiv) were reacted for 2.5 h to give complete conversion of 17 to a 80:20

mixture of 18 (98:2 dr):(19–22).

Table 2 Entry 8



1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), 2,6-lutidine N-oxide (25.2 mg,

23 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17

(38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted for 2 h to give complete conversion of 17

to a 80:20 mixture of 18 (99:1 dr):(19–22).




General Procedure III: Survey of Diaryl Diselenides with (E)-1-Benzyloxyl-4-hexene (17)

(Table 2, Entries 9–12)


glovebox and charged sequentially with the requisite diaryl diselenide [(ArylSe)2] (0.01 mmol, 5


fluoropyridinium tetrafluoroborate 11 (48.0 mg, 0.26 mmol, 1.3 equiv), and was then sealed with

a rubber septum, removed from the box, and placed under argon via an inlet needle. MeCN-d3

(1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), and

chlorotrimethylsilane (Me3SiCl) (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv) were then added

sequentially via syringe and stirring was commenced. After ca. 10 min, (E)-1-benzyloxyl-4-

hexene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) was added via syringe, then the argon inlet

needle was removed and the resultant suspension was stirred at rt. Once the reaction mixture had

become homogeneous, it was stirred for a further ca. 15 min and an aliquot (0.5 mL) was

transferred via syringe into an oven-dried NMR tube. The reaction mixture was then analyzed by 1H NMR spectroscopy in order to assess the ratio of product 18 to by-products 19–22, and to

determine the syn/anti diastereoisomeric ratio (dr) for 18 (by comparison to an authentic sample

of the anti-diastereoisomer of 18). Relative ratios were determined using diagnostic 1H NMR

resonances for product 18 and by-products 19–22.




Survey of Diaryl Diselenides (Table 2)

Table 2 Entry 9

Following General Procedure III, bis[3,5-bis(trifluoromethyl)phenyl] diselenide 24 (5.8

mg, 0.01 mmol, 5 mol %), BnEt3NCl (138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol,

1.3 equiv), MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv),

Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0

equiv) were reacted for 10 h to give complete conversion of 17 to a 58:42 mixture of 18 (88:12

dr):(19–22).

Table 2 Entry 10

Following General Procedure III, bis(2-nitrophenyl) diselenide 25 (4.0 mg, 0.01 mmol, 5

mol %), BnEt3NCl (138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv), MeCN-

d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2

mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were

reacted for 18 h to give complete conversion of 17 to a 59:41 mixture of 18 (55:45 dr):(19–22).




Table 2 Entry 11

Following General Procedure III, bis(4-methoxyphenyl) diselenide 26 (3.7 mg, 0.01

mmol, 5 mol %), BnEt3NCl (138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg, 0.26 mmol, 1.3 equiv),

MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), Me3SiCl


were reacted for 3.5 h to give complete conversion of 17 to a 90:10 mixture of 18 (99:1 dr):(19–

22).

Table 2 Entry 12

Following General Procedure III, bis(2-methoxyphenyl) diselenide 27 (3.7 mg, 0.01




were reacted for 8 h to give complete conversion of 17 to a 83:17 mixture of 18 (98:2 dr):(19–

22).





entry substrate A

PhSeSePh (5 mol %)

B PhSeSePh (5 mol %)

& 23 (1.0 equiv)

C 26

(5 mol %)

1

19 h (83%) >99:1 dr

89:11

8 h (73%) >99:1 dr 98.5:1.5

10 h (73%) >99:1 dr

96:4

2

7 h (61%) 97:3 dr 80:20

4 h (81%) >98:2 dr

88:12

6 h (83%) >97:3 dr

92:8

3

6 h (79%) 99:1 dr 82:18

3 h (79%) >99:1 dr

94:6

3.5 h (74%) >98:2 dr

85:15

4

14 h (91%) >99:1 dr

n.d.a

9 h (66%) 99:1 dr

n.d.a

12 h (65%) >98:2 dr

93:7

5

7 h (64%) >99:1 dr

78:22

5 h (77%) 99:1

81:19

–b

6

5 h (91%) 90:10

3 h (90%) 90:10

–b

7

6 h (73%) 99:1 dr 80:20

2 h (79%) 99:1 dr 80:20

5 hc (71%) 99:1 dr 85:15

NMR yields, given in parentheses, were measured against 1,1,2,2-tetrachloroethane (1.0 equiv) as an internal standard. In all cases ≥93% of the alkene starting material was consumed. The ratios of product to by-products in the crude reaction mixtures are given in italics. a Ratio of product to by-products could not be determined (n.d.) via 1H NMR spectroscopy. b Pre-catalyst 26 was not surveyed in the catalytic syn-dichlorination of alkenes 28r and 28d. c 2,6-Lutidine N-oxide 23 (1.0 equiv) was added to the reaction mixture with pre-catalyst 26 in the catalytic syn-dichlorination of alkene 17.






glovebox and charged sequentially with the requisite diaryl diselenide [(ArylSe)2] (0.01 mmol, 5


fluoropyridinium tetrafluoroborate 11 (48.0 mg, 0.26 mmol, 1.3 equiv), and was then sealed with

a rubber septum, removed from the box, and placed under argon via an inlet needle. MeCN-d3

(1.0 mL) and 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv) were then added

and stirring was commenced. 2,6-Lutidine N-oxide 23 (25.2 mg, 23 µL, 0.20 mmol, 1.0 equiv)

was added (for condition B, entries 1–7, and condition C, entry 7), followed by

chlorotrimethylsilane (Me3SiCl) (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), both via syringe. After

ca. 10 min, the alkene substrate (0.20 mmol) was transferred via syringe to the reaction mixture

[for alkenes of unknown density, only 0.6 mL of MeCN-d3 was added initially and the remaining

0.4 mL (in two 0.2 mL portions) was used to transfer the alkene across from an oven-dried, 4 mL

dram vial under an argon atmosphere, via syringe]. The argon inlet needle was then removed, the

rubber septum sealed, and the resultant suspension was stirred at rt. At the time stated, an aliquot

(0.5 mL) was transferred via syringe into an oven-dried NMR tube, and the reaction was

analyzed by 1H NMR spectroscopy to measure the NMR yield, syn/anti diastereoisomeric ratio

(dr) and product to by-products ratio via diagnostic 1H NMR resonances (in the range δ 5.9–4.0).

Table S1 Condition A Entry 1

Following General Procedure IV, PhSeSePh (3.1 mg, 0.01 mmol, 5 mol %), BnEt3NCl




for 19 h to give complete conversion to a 89:11 mixture of 7 (83% NMR yield, >99:1 dr):8.

(Note: see General Procedure I for diagnostic 1H NMR resonances for 7 and 8).




Table S1 Condition B Entry 1



1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), 2,6-lutidine N-oxide 23 (25.2

mg, 23 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and

cyclohexene 6 (16.4 mg, 20 µL, 0.20 mmol, 1.0 equiv) were reacted for 8 h to give 96%

conversion to a 98.5:1.5 mixture of 7 (73% NMR yield, >99:1 dr):8. (Note: see General

Procedure I for diagnostic 1H NMR resonances for 7 and 8).

Table S1 Condition C Entry 1

Following General Procedure IV, bis(4-methoxyphenyl) diselenide 26 (3.7 mg, 0.01



(44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and cyclohexene 6 (16.4 mg, 20 µL, 0.20 mmol, 1.0

equiv) were reacted for 8 h to give 95% conversion to a 96:4 mixture of 7 (73% NMR yield,

>99:1 dr):8. (Note: see General Procedure I for diagnostic 1H NMR resonances for 7 and 8).








0.41 mmol, 2.0 equiv), and alkene 28q (67.7 mg, 0.20 mmol, 1.0 equiv) were reacted for 7 h to

give complete conversion to a 80:20 mixture of 29q (61% NMR yield, 97:3 dr):(S7–S9). [Note:

the diagnostic 1H NMR chemical shifts for (S7 + S8 + S9) were tentatively assigned].

Data for 29q: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.51 (ddd, J = 8.2, 5.4, 2.2 Hz, 1 H, HC(3)), 4.25 (ddd, J = 7.9, 5.9, 2.2 Hz, 1 H,

HC(2))

Data for the anti-diastereoisomer of 29q: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.37 (ddd, J = 9.5, 6.3, 2.8 Hz, 1 H, HC(3)), 4.22 (dt, J = 6.4, 4.8 Hz, 1 H, HC(2))




Data for (S7–S9): 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 5.87–5.78, 5.69–5.62, 5.57–5.46 (m, 1 H for S7, 1 H for S8, 2 H for S9, HC(3) for

S7, HC(2) for S8, HC(3,4) for S9)





mg, 23 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene

28q (67.7 mg, 0.20 mmol, 1.0 equiv) were reacted for 4 h to give complete conversion to a 88:12

mixture of 29q (81% NMR yield, >98:2 dr):(S7–S9). The by-product giving rise to the 1H signal

at δ 5.69–5.62 was only present in a trace amount. [Note: the diagnostic 1H NMR chemical shifts

for (S7–S9) were tentatively assigned].








(44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 28q (67.7 mg, 0.20 mmol, 1.0 equiv) were

reacted for 6 h to give complete conversion to a 92:8 mixture of 29q (83% NMR yield, >97:3

dr):(S7–S9). The by-product giving rise to the 1H signal at δ 5.69–5.62 was absent. [Note: the

diagnostic 1H NMR chemical shifts for (S7–S9) were tentatively assigned].








0.41 mmol, 2.0 equiv), and alkene 28h (38.1 mg, 0.20 mmol, 1.0 equiv) were reacted for 6 h to

give complete conversion to a 82:18 mixture of 29h (79% NMR yield, 99:1 dr):(S10 + S11 + 21

+ 22). S10 and S11 were the major by-products observed.

Data for 29h: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)


HC(4))

Data for the anti-diastereoisomer of 29h: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)


HC(4))

Data for (S10 + S11 + 21 + 22): 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 5.88 (ddd, J = 16.9, 10.2, 8.2 Hz, 1 H, HC(5) for 21), 5.77–5.70 & 5.68–5.62 (m,

2 H, HC(3,4) for 22), 5.59–5.50 (m, 1 H for S10, 1 H for S11, HC(5) for S10,

HC(4) for S11), 5.25 (dt, J = 17.0, 1.2 Hz, 1 H, HC(6) for 21), 5.13–5.09 (m, 1 H,

HC(6) for 21)









28h (38.1 mg, 0.20 mmol, 1.0 equiv) were reacted for 3 h to give complete conversion to a 94:6

mixture of 29h (79% NMR yield, >99:1 dr):(S10 + S11 + 21 + 22). S10 and S11 were the major

by-products observed, while 21 and 22 were only present in trace amounts under these

conditions.





(44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 28h (38.1 mg, 0.20 mmol, 1.0 equiv) were

reacted for 3.5 h to give complete conversion to a 85:15 mixture of 29h (74% NMR yield, >98:2

dr):(S10 + S11 + 21 + 22). S10 and S11 were the major by-products observed.








0.41 mmol, 2.0 equiv), and alkene 28t (20.0 mg, 24 µL, 0.20 mmol, 1.0 equiv) were reacted for

14 h to give complete conversion to a mixture of 29t (91% NMR yield, >99:1 dr), S12, S13, and

S14. Unfortunately the ratio 29t:(S12–S14) could not be determined due to signal overlap.

Data for 29t: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.48–4.43 (m, 1 H, HC(3)), 4.29 (ddd, J = 7.9, 6.0, 2.1 Hz, 1 H, HC(2))

Data for the anti-diastereoisomer of 29t: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.25–4.20 (m, 2 H, HC(2,3))






28t (20.0 mg, 24 µL, 0.20 mmol, 1.0 equiv) were reacted for 9 h to give ~93% conversion to a

mixture of 29t (66% NMR yield, 99:1 dr), S12, S13, and S14. Unfortunately the ratio 29t:(S12–

S14) could not be determined due to signal overlap from unidentified background reactions.








(44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 28t (20.0 mg, 24 µL, 0.20 mmol, 1.0 equiv)

were reacted for 12 h to give ~96% conversion to a 93:7 mixture of 29t (65% NMR yield, >98:2

dr):( S12–S14). [Note: the diagnostic 1H NMR chemical shifts for (S12–S14) were tentatively

assigned].


δ 5.84–5.76, 5.66–5.56, 5.53–5.47 (m, 1 H for S12, 1 H for S13, 2 H for S14,

HC(3) for S12, HC(2) for S13, HC(3,4) for S14)








0.41 mmol, 2.0 equiv), and alkene 28r (67.7 mg, 0.20 mmol, 1.0 equiv) were reacted for 7 h to

give complete conversion to a 78:22 mixture of 29r (64% NMR yield, >99:1 dr):(S15 + S16 +

S9). [Note: the diagnostic 1H NMR chemical shifts for (S15 + S16 + S9) were tentatively

assigned].

Data for 29r: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.37 (ddd, J = 9.5, 6.3, 2.8 Hz, 1 H, HC(3)), 4.22 (dt, J = 6.4, 4.8 Hz, 1 H, HC(2))

Data for the anti-diastereoisomer of 29r: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)


HC(2))




Data for (S15 + S16 + S9): 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 5.8–5.81, 5.78–5.70, 5.63–5.54 (m, 1 H for S15, 1 H for S16, 2 H for S9, HC(3)

for S15, HC(2) for S16, HC(3,4) for S9)






28r (67.7 mg, 0.20 mmol, 1.0 equiv) were reacted for 5 h to give complete conversion to a 81:19

mixture of 29r (77% NMR yield, 99:1 dr):(S15 + S16 + S9). [Note: the diagnostic 1H NMR

chemical shifts for (S15 + S16 + S9) were tentatively assigned].








0.41 mmol, 2.0 equiv), and alkene 28d (62.1 mg, 0.20 mmol, 1.0 equiv) were reacted for 5 h to

give complete conversion to a 90:10 mixture of 29d (91% NMR yield):(S17–S19). [Note: the

diagnostic 1H NMR chemical shifts for (S17–S19) were tentatively assigned].

Data for 29d: 1H NMR: (500 MHz, MeCN-d3, diagnostic resonances only)

δ 4.45 (dtd, J = 9.3, 5.5, 3.6 Hz, 1 H, HC(3))


δ 6.18–6.16 (m, 1 H, HC(4) for S17), 6.12–6.08 (m, 1 H, HC(3) for S17), 5.95–5.86

(m, 2 H, HC(2,3) for S19), 5.03 (dq, J = 17.2, 1.7 Hz, 1 H, HC(4) for S18), 4.98

(ddt, J = 10.3, 2.3, 1.1 Hz, 1 H, HC(4) for S18)









28d (62.1 mg, 0.20 mmol, 1.0 equiv) were reacted for 3 h to give >95% conversion to a 90:10

mixture of 29d (90% NMR yield):(S17–S19). [Note: the diagnostic 1H NMR chemical shifts for

(S17–S19) were tentatively assigned].







MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), 2,6-

lutidine N-oxide 23 (25.2 mg, 23 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41

mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted for 18 h to

give ~99% conversion to a 85:15 mixture of 18 (72% NMR yield, 99:1 dr):(19–22). Earlier time

points taken at 3 h and 5 h showed 61% and 71% NMR yields of 18, respectively, with the same

85:15 ratio of 18:(19–22) in both cases.


[Note: Reagents were selectively omitted from the following procedure as described in

the various control experiments below]. An oven-dried, 4-mL dram vial equipped with a

magnetic stirrer bar was taken into the glovebox and charged sequentially with diphenyl

diselenide (PhSeSePh) (3.4 mg, 0.01 mmol, 5 mol %), benzyltriethylammonium chloride

(BnEt3NCl) (138 mg, 0.60 mmol, 3.0 equiv), and N-fluoropyridinium tetrafluoroborate 11 (48.0

mg, 0.26 mmol, 1.3 equiv), and was then sealed with a rubber septum, removed from the box,

and placed under argon via an inlet needle. MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3

mg, 21 µL, 0.20 mmol, 1.0 equiv), 2,6-lutidine N-oxide 23 (25.2 mg, 23 µL, 0.20 mmol, 1.0

equiv), and chlorotrimethylsilane (Me3SiCl) (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv) were then

added sequentially and stirring was commenced. After ca. 10 min, (E)-1-benzyloxyl-4-hexene 17

(38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) was transferred via syringe to the reaction mixture. The

argon inlet needle was then removed, the rubber septum sealed, and the resultant suspension was

stirred at rt. At the time stated, an aliquot (0.1 mL) was transferred via syringe into an oven-dried

NMR tube and was diluted with MeCN-d3 (0.4 mL), then the reaction was analyzed by 1H NMR

spectroscopy.




Control Experiment I – Omission of PhSeSePh

Following General Procedure V, BnEt3NCl (138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg,


mmol, 1.0 equiv), 23 (25.2 mg, 23 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41

mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted. After 20

h, 50% conversion of 17 had occurred to give the anti-diastereomer of 29h (40% NMR yield)

and allylic chloride 21 (6% NMR yield) as the main by-product (based on the diagnostic 1H

NMR resonance for 21 described in General Procedure II). After 40 h, 86% conversion of 17 had

occurred to give the anti-diastereoisomer of 29h (60% NMR yield) and 21 (8% NMR yield).

Control Experiment II – Omission of PhSeSePh and 2,6-Lutidine N-Oxide 23

Following General Procedure V, BnEt3NCl (138 mg, 0.60 mmol, 3.0 equiv), 11 (48.0 mg,


mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL, 0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39

µL, 0.20 mmol, 1.0 equiv) were reacted. After 20 h, 46% conversion of 17 had occurred to give

the anti-diastereoisomer of 29h (38% NMR yield) and allylic chloride 21 (7% NMR yield) as the

main by-product (based on the diagnostic 1H NMR resonance for 21 described in General

Procedure II). After 40 h, complete conversion of 17 had occurred to give the anti-

diastereoisomer of 29h (74% NMR yield) and 21 (10% NMR yield).




Control Experiment III – Omission of N-Fluoropyridinium Tetrafluoroborate 11

Following General Procedure V, PhSeSePh (3.4 mg, 0.01 mmol, 5 mol %), BnEt3NCl

(138 mg, 0.60 mmol, 3.0 equiv), MeCN-d3 (1.0 mL), 1,1,2,2-tetrachloroethane (33.3 mg, 21 µL,

0.20 mmol, 1.0 equiv), 23 (25.2 mg, 23 µL, 0.20 mmol, 1.0 equiv), Me3SiCl (44.2 mg, 52 µL,

0.41 mmol, 2.0 equiv), and alkene 17 (38.1 mg, 39 µL, 0.20 mmol, 1.0 equiv) were reacted.

After either 20 h or 40 h, no conversion of 17 had occurred.

General Procedure VI: NMR Spectroscopic Studies on Catalytic, syn-Dichlorination of

Volatile Alkenes

An oven-dried, 10-mL Schlenk flask equipped with a magnetic stirrer bar was taken into

the glovebox and charged sequentially with diphenyl diselenide (PhSeSePh) (15.8 mg, 0.05

mmol, 5 mol %), benzyltriethylammonium chloride (BnEt3NCl) (690 mg, 3.03 mmol, 3.0 equiv),

and N-fluoropyridinium tetrafluoroborate 11 (240 mg, 1.30 mmol, 1.3 equiv), and was then

sealed with a rubber septum, removed from the box, and placed under argon. MeCN-d3 (5.0 mL),

1,1,2,2-tetrachloroethane (168 mg, 106 µL, 1.00 mmol, 1.0 equiv), 2,6-lutidine N-oxide 23 (126

mg, 115 µL, 1.02 mmol, 1.0 equiv), and chlorotrimethylsilane (Me3SiCl) (218 mg, 255 µL, 2.01

mmol, 2.0 equiv) were then added sequentially and stirring was commenced. After ca. 10 min, an

off-white suspension (occasionally with yellow tinges) was observed. At this point, the requisite

alkene (1.00 mmol, 1.0 equiv) was transferred via syringe to the reaction mixture, and the

resultant suspension was stirred at rt. At the time stated, stirring was interrupted to let any solids

settle to the bottom of the flask and an aliquot (0.5 mL) was transferred via syringe into an oven-

dried NMR tube. The reaction was analyzed by 1H NMR spectroscopy to determine the NMR

yield and syn/anti diastereoisomeric ratio (dr).




NMR Study on Formation of (u)-1,2-Dichlorocyclohexane (7)

Following General Procedure VI, PhSeSePh (15.8 mg, 0.05 mmol, 5 mol %), BnEt3NCl

(690 mg, 3.03 mmol, 3.0 equiv), 11 (240 mg, 1.30 mmol, 1.3 equiv), MeCN-d3 (5.0 mL),

1,1,2,2-tetrachloroethane (174 mg, 110 µL, 1.04 mmol, 1.0 equiv), 23 (126 mg, 115 µL, 1.02

mmol, 1.0 equiv), Me3SiCl (218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and cyclohexene 6 (85.2

mg, 105 µL, 1.04 mmol, 1.0 equiv) were reacted for 10 h to give a red-brown suspension.

Analysis by 1H NMR spectroscopy showed almost complete conversion of cyclohexene 6 had

occurred to give (u)-1,2-dichlorocyclohexane 7 (80% NMR yield, >99:1 dr) and allylic chloride

by-product 8 (4% NMR yield). (Note: For diagnostic 1H NMR resonances for 7 and 8 see

General Procedure I). Extension of the reaction time to 24 h gave complete consumption of

cyclohexene 6 but only a negligible increase in the amount of 7 (82% NMR yield, >99:1 dr) and

8 (6% NMR yield).

NMR Study on Formation of (u)-1,2-Dichlorocycloheptane (29a)




mmol, 1.0 equiv), Me3SiCl (218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and cycloheptene 28a (98.9

mg, 120 µL, 1.03 mmol, 1.0 equiv) were reacted for 4 h to give a red-brown suspension.

Analysis by 1H NMR spectroscopy showed complete conversion of cycloheptene 28a had

occurred to give (u)-1,2- dichlorocycloheptane 29a (96% NMR yield, 99:1 dr) and allylic

chloride by-product S22 (ca. 3% NMR yield).




Data for 29a: 1H NMR: (400 MHz, MeCN-d3, diagnostic resonances only)

δ 4.52–4.47 (m, 2 H, HC(1,2))

Data for the anti-diastereoisomer of 29a: 1H NMR: (400 MHz, MeCN-d3, diagnostic resonances only)

δ 4.33–4.28 (m, 2 H, HC(1,2))

Data for S20: 1H NMR: (400 MHz, MeCN-d3, diagnostic resonances only)

δ 5.86–5.76 (m, 2 H, HC(2,3))

NMR Study on Formation of (l)-4,5-Dichlorooctane (29g)




mmol, 1.0 equiv), Me3SiCl (218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and (E)-4-octene 28g (98.9

mg, 160 µL, 1.02 mmol, 1.0 equiv) were reacted for 4 h to give an orange-red suspension.

Analysis by 1H NMR spectroscopy showed complete conversion of (E)-4-octene 28g had

occurred to give (l)-4,5-dichlorooctane 29g (66% NMR yield, 99:1 dr) and tentatively assigned

vinylic and allylic chlorides by-products (S21 + S22) (ca. 34% combined yield).

Data for 29g: 1H NMR: (400 MHz, MeCN-d3, diagnostic resonances only)

δ 4.20–4.14 (m, 2 H, HC(4,5))




Data for the anti-diastereoisomer of 29g: 1H NMR: (400 MHz, MeCN-d3, diagnostic resonances only)

δ 4.00–3.96 (m, 2 H, HC(4,5))

Data for (S21 + S22): 1H NMR: (400 MHz, MeCN-d3, diagnostic resonances only)

δ 5.76 & 5.73 (t, J = 6.4 Hz, 1 H, HC(4) for S22), 5.58 (t, J = 7.8 Hz, 1 H, HC(5)

for S21), 5.51 & 5.47 (dt, J = 8.9, 1.5 Hz, 1 H, HC(3) for S22)

General Procedure VII: Catalytic, syn-Dichlorination of Alkenes with 2,6-Lutidine N-

Oxide as Additive (Table 3)





sealed with a rubber septum, removed from the box, and placed under argon. MeCN (5.0 mL),

2,6-lutidine N-oxide 23 (126 mg, 115 µL, 1.02 mmol, 1.0 equiv), and chlorotrimethylsilane

(Me3SiCl) (218 mg, 255 µL, 2.01 mmol, 2.0 equiv) were then added sequentially and stirring

was commenced. After ca. 10 min, an off-white suspension (occasionally with yellow tinges)

was observed. At this point, the requisite alkene (1.00 mmol, 1.0 equiv) was transferred via

syringe to the reaction mixture [for alkenes of unknown density, only 3.0 mL of MeCN was

added initially and the remaining 2.0 mL (in two 1.0 mL portions) was used to transfer the

alkene across from an oven-dried, 4-mL dram vial under an argon atmosphere, via syringe]. The

resultant suspension was stirred at rt, and was monitored by TLC until no alkene substrate could

be detected. Once the reaction had reached completion, sat. aq. NaHCO3 (1.0 mL) was added to

quench any unreacted chlorotrimethylsilane. After stirring for ca. 10 min at rt, the resultant

mixture was transferred to a separatory funnel and diluted with H2O (15 mL). The aqueous layer

was extracted with Et2O (3 × 15 mL), and the combined organic extracts were washed with brine

(15 mL), then dried (MgSO4), filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg for

non-volatile products or 5–8 °C, ca. 20 mm Hg for volatile products). The resultant residue was




re-dissolved in Et2O (5.0 mL) and eluted through a short plug of silica gel (ca. 0.55 g SiO2

packed into a Pasteur pipet to a height of ca. 40 mm) in order to partially remove 2,6-lutidine N-

oxide and any ammonium salts, and the plug was then rinsed through with further portions of

Et2O (3 × 5 mL). The solvent was removed in vacuo (20–23 °C, ca. 20 mm Hg for non-volatile

products or 5–8 °C, ca. 20 mm Hg for volatile products), and an aliquot of the crude mixture was

dissolved in CDCl3 to measure the syn/anti diastereoisomeric ratio (dr) by 1H NMR spectroscopy.

The syn-dichloride product was then isolated as described.

Preparation of (u)-1,2-Dichlorocyclohexane (7) (Table 3)

Following General Procedure VII (but on double the scale in a 25-mL Schlenk flask),

PhSeSePh (31.4 mg, 0.10 mmol, 5 mol %), BnEt3NCl (1.375 g, 6.04 mmol, 3.0 equiv), 11 (486

mg, 2.63 mmol, 1.3 equiv), MeCN (10.0 mL), 23 (246 mg, 225 µL, 2.00 mmol, 1.0 equiv),

Me3SiCl (445 mg, 520 µL, 4.10 mmol, 2.0 equiv), and cyclohexene 6 (166 mg, 205 µL, 2.02

mmol, 1.0 equiv) were reacted for 10 h. (Note: TLC was indeterminate in this case due to the

volatility of cyclohexene and the reaction time was instead based on a previous test reaction

monitored by 1H NMR spectroscopy). A red-brown suspension was obtained which, following

the work-up described in the general procedure, gave an orange oil (>99:1 dr). Caution: the

product is volatile and should not be left on the rotary evaporator for an extended period.


loaded, petroleum ether (500 mL), ca. 10 mL fractions] gave a yellow oil (174 mg, ca. 95%

purity) (N.B. solvent was removed in vacuo at 5–8 °C, ca. 20 mm Hg). Further purification via

Kugelrohr distillation at reduced pressure (15 mm Hg) gave 7 as a clear, colorless oil (156 mg,

51%).

Data for 7: bp: 90 °C (ABT) (15 mm Hg)





δ 4.29–4.27 (m, 2 H, HC(1,2)), 2.15–2.09 (m, 2 H, HC(3,6)), 1.89–1.83 (m, 2 H,

HC(3,6)), 1.83–1.76 (m, 2 H, HC(4,5)), 1.46–1.39 (m, 2 H, HC(4,5)) 13C NMR: (126 MHz, CDCl3)

δ 62.7 (C(1,2)), 32.3 (C(3,6)), 22.1 (C(4,5))

IR: (neat)

2944 (s), 2856 (m), 1447 (m), 1356 (w), 1313 (w), 1290 (w), 1274 (m), 1227 (w),

1192 (w), 1132 (w), 1084 (w), 1056 (w), 1267 (w), 986 (m), 907 (m), 877 (m), 834

(m), 817 (m), 741 (m), 694 (m)

MS: (EI+, TOF)

154.0 (18), 152.0 (M+, 30), 118.0 (26), 116.0 (100), 90.0 (11), 88.0 (23), 81.6 (20),

81.1 (27), 80.0 (53), 79.0 (81), 77.0 (15), 75.0 (53), 67.1 (52), 62.0 (12), 55.1 (16),

54.0 (13), 53.0 (15)

HRMS: (EI+, TOF)

calcd for C6H10Cl2 (M+): 152.0160, found: 152.0161

TLC: Rf 0.44 (hexane) [CAM; developed at <300 °C, white spot against yellow

background which quickly disappeared with further and/or stronger heating]

Analysis: C6H10Cl2 (153.05)

Calcd: C, 47.09; H, 6.59%

Found: C, 47.05; H, 6.51%

Preparation of (u)-1,2-Dichlorocycloheptane (29a) (Table 3)




Me3SiCl (445 mg, 520 µL, 4.10 mmol, 2.0 equiv), and cycloheptene 28a (194 mg, 235 µL, 2.01




mmol, 1.0 equiv) were reacted for 4 h to give a red-brown suspension which, following the

work-up described in the general procedure, gave an orange-red oil (99:1 dr). Caution: the

product is volatile and should not be left on the rotary evaporator for an extended period.

Purification via flash column chromatography [27 g high porosity grade SiO2, 24 mm Ø,

wet loaded, pentane (500 mL), ca. 10 mL fractions] gave a yellow oil (268 mg) (N.B. solvent

was removed in vacuo at 5–8 °C, ca. 20 mm Hg). Further purification via two successive

Kugelrohr distillations at reduced pressure (10 mm Hg) gave 29a as a clear, colorless oil (256

mg, 77%).

Data for 29a: bp: 118 °C (ABT) (10 mm Hg)


δ 4.41–4.39 (m, 2 H, HC(1,2)), 2.22–2.15 (m, 2 H, HC(3,7)), 2.01–1.94 (m, 2 H,

HC(3,7)), 1.81–1.68 (m, 3 H, HC(4,5,6)), 1.62–1.46 (m, 3 H, HC(4,5,6)) 13C NMR: (126 MHz, CDCl3)

δ 66.2 (C(1,2)), 34.1 (C(3,7)), 25.6 (C(5)), 23.4 (C(4,6))

IR: (neat)

2936 (s), 2863 (m), 2693 (w), 1455 (m), 1434 (w), 1361 (s), 1315 (s), 1285 (w),

1233 (w), 1196 (w), 1150 (w), 1047 (w), 1004 (w), 977 (w), 942 (w), 915 (w), 882

(w), 863 (w), 840(w), 822 (w), 795 (w), 769 (w), 716 (w), 685 (m), 643 (w)

MS: (CI+, DFSF)

131.0 ([M–Cl]+, 7), 129.0 ([(M–HCl)-H]+, 6), 96.1 ([M–2Cl]+, 25), 95.1 ([(M–

HCl)–Cl]+, 100), 94.1 (22), 81.1 (11), 79.1 (12), 68.0 (12), 63.0 (27), 59.0 (12),

55.0 (12)

HRMS: (CI+, DFSF)

calcd for C7H10Cl [(M–HCl)-H]+: 129.04721, found: 129.04710



Analysis: C7H12Cl2 (167.07)

Calcd: C, 50.32; H, 7.24%

Found: C, 50.58; H, 7.02%




Preparation of [1r-(u)-3,4-Dichlorocyclopentyl]methyl acetate (29b) (Table 3)

Following General Procedure VII, PhSeSePh (15.8 mg, 0.05 mmol, 5 mol %), BnEt3NCl

(690 mg, 3.03 mmol, 3.0 equiv), 11 (242 mg, 1.31 mmol, 1.3 equiv), MeCN (5.0 mL), 23 (126

mg, 115 µL, 1.02 mmol, 1.0 equiv), Me3SiCl (218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and

alkene 28b (141 mg, 1.01 mmol, 1.0 equiv) were reacted for 24 h (TLC analysis showed that a

trace amount of 28b remained). Following the work-up described in the general procedure, a

89:11 mixture of dichlorides 29b [diastereoisomeric at C(1)] was obtained as an orange oil

(>99:1 syn/anti dichloride ratio w.r.t. the major diastereoisomer). Purification via flash column

chromatography [74 g SiO2, 34 mm Ø, dry loaded with 2.4 g SiO2, 92:8 hexane/EtOAc (1 L), ca.

10 mL fractions] gave a colourless oil [159 mg, 91:9 dr at C(1)]. Caution: the product is volatile

at ca. 0.05 mm Hg. Further purification via Kugelrohr distillation at reduced pressure (0.05 mm

Hg) gave 29b as a clear, colorless oil [155 mg, 73%, 91:9 dr at C(1)]. By analogy to known syn-

and anti-epoxy ethers of 1-hydroxymethyl-3-cyclopentene,26 the relative configuration at C(1) in

29b was determined by chemical correlation with 29c [which was compared to an authentic

sample (vide infra)]. HC(6) of the major syn-diastereoisomer [at C(1)] has a larger vicinal 1H-1H 3J coupling constant (3Jsyn = 7.2 Hz versus 3Janti = 6.0 Hz) and is shifted downfield [δ HC(6)syn =

4.11 versus δ HC(6)anti = 3.99] than HC(6) of the corresponding minor anti-diastereoisomer [at

C(1)].

Data for 29b: bp: 71 °C (ABT) (0.05 mm Hg)


δ 4.36–4.33 (m, 2 H, HC(3,4), minor diastereoisomer), 4.31–4.28 (m, 2 H, HC(3,4),

major diastereoisomer), 4.11 (d, J = 7.2 Hz, 2 H, HC(6), major diastereoisomer),

3.99 (d, J = 6.0 Hz, 2 H, HC(6), minor diastereoisomer), 2.85–2.77 (m, 1 H, HC(1),

minor diastereoisomer), 2.47–2.26 (m, 3 H for major diastereoisomer, 2 H for

minor diastereoisomer, HC(1) for major diastereoisomer, HC(2,5) for both

diastereoisomers), 2.06 (s, 3 H, HC(8), minor diastereoisomer), 2.05 (s, 3 H, HC(8),




major diastereoisomer), 2.03–1.91 (m, 2 H each, HC(2,5), both diastereoisomers) 13C NMR: (126 MHz, CDCl3)

δ 170.9 (C(7), both diastereoisomers), 68.1 (C(6), major diastereoisomer), 66.9

(C(6), minor diastereoisomer), 62.6 (C(3,4), minor diastereoisomer), 62.0 (C(3,4),

major diastereoisomer), 36.1 (C(2,5), major diastereoisomer), 36.0 (C(2,5), minor

diastereoisomer), 34.2 (C(1), major diastereoisomer), 33.7 (C(1), minor

diastereoisomer), 20.9 (C(8), both diastereoisomers)

IR: (neat)

3445 (w), 2976 (w), 2951 (w), 2898 (w), 2856 (w), 1741 (s), 1441 (m), 1388 (w),

1367 (m), 1311 (w), 1239 (s), 1135 (m), 1042 (m), 996 (w), 950 (w), 893 (w), 794

(w), 640 (w), 614 (w)

MS: (ESI+, TOF)

235.0 (30), 233.0 ([M+Na]+, 45), 209.0 (33), 208.0 (16), 207.2 (34), 207.0 (87),

206.0 (20), 205 (100), 187 (10)

HRMS: (ESI+, TOF)

calcd for C8H12Cl2NaO2 [M+Na]+: 233.0112, found: 233.0112


Analysis: C8H12Cl2O2 (211.08)

Calcd: C, 45.52; H, 5.73%

Found: C, 45.55; H, 5.57%

Preparation of tert-Butyl{[1r-(u)-3,4-dichlorocyclopentyl]methoxy}diphenylsilane (29c)

(Table 3)







alkene 28c (337 mg, 1.00 mmol, 1.0 equiv) were reacted for 16 h to give an orange suspension

which, following the work-up described in the general procedure, gave a 91:9 mixture of

dichlorides 29c [diastereoisomeric at C(1)] as an orange oil (>99:1 syn/anti dichloride ratio w.r.t.

the major diastereoisomer). Purification via flash column chromatography [48 g high porosity

grade SiO2, 30 mm Ø, dry loaded with 1.8 g SiO2, 98:2 petroleum ether/MTBE (700 mL), ca. 10

mL fractions] gave a colourless oil [292 mg, 91:9 dr at C(1)]. Further purification via Kugelrohr

distillation at reduced pressure (0.05 mm Hg) gave 29c as a clear, colorless, viscous oil [288 mg,

71%, 91:9 dr at C(1)]. The relative configuration at C(1) in 29c was determined by comparison

with authentic samples of both diastereoisomers obtained via deoxochlorination of the

corresponding epoxides under Appel-type conditions.27

Data for 29c: bp: 186 °C (ABT) (0.05 mm Hg)


δ 7.68–7.62 (m, 4 H each, HC(2′,2′′), both diastereoisomers), 7.46–7.37 (m, 6 H

each, HC(3′,4′,3′′,4′′), both diastereoisomers), 4.39–4.36 (m, 2 H, HC(3,4), minor

diastereoisomer), 4.31–4.26 (m, 2 H, HC(3,4), major diastereoisomer), 3.69 (d, J =

6.8 Hz, 2 H, HC(6), major diastereoisomer), 3.57 (d, J = 5.0 Hz, 2 H, HC(6), minor

diastereoisomer), 2.70–2.62 (m, 1 H, HC(1), minor diastereoisomer), 2.37–2.20 (m,

3 H for major diastereoisomer, 2 H for minor diastereoisomer, HC(1) for major

diastereoisomer, HC(2,5) for both diastereoisomers), 2.10–1.98 (m, 2 H each,

HC(2,5), both diastereoisomers), 1.06 (s, 9 H, Sit-Bu, both diastereoisomers) 13C NMR: (126 MHz, CDCl3)

δ 135.5 (C(2′,2′′), both diastereoisomers), 133.6 (C(1′,1′′), major diastereoisomer),

133.3 (C(1′,1′′), minor diastereoisomer), 129.8 (C(4′,4′′), minor diastereoisomer),

129.6 (C(4′,4′′), major diastereoisomer), 127.74 (C(3′,3′′), minor diastereoisomer),

127.66 (C(3′,3′′), major diastereoisomer), 67.9 (C(6), major diastereoisomer), 66.2

(C(6), minor diastereoisomer), 63.4 (C(3,4), minor diastereoisomer), 62.3 (C(3,4),

major diastereoisomer), 37.7 (C(1), major diastereoisomer), 36.8 (C(1), minor

diastereoisomer), 35.9 (C(2,5), major diastereoisomer), 35.7 (C(2,5), minor

diastereoisomer), 26.87 (SiCMe3, minor diastereoisomer), 26.82 (SiCMe3, major

diastereoisomer), 19.3 (SiCMe3, both diastereoisomers)




IR: (neat)

3071 (m), 3050 (w), 2931 (m), 2894 (w), 2858 (m), 2742 (w), 1961 (w), 1893 (w),

1824 (w), 1590 (w), 1472 (m), 1428 (m), 1388 (w), 1361 (w), 1312 (w), 1277 (w),

1257 (w), 1112 (s), 1030 (w), 1008 (w), 998 (w), 975 (w), 949 (w), 916 (w), 892

(w), 824 (m), 798 (m), 740 (m), 702 (m), 642 (w), 613 (m)

MS: (ESI+, TOF)

407.2 ([M+H]+, 10), 339.4 (25), 338.4 ([M–2Cl]+, 100), 284.3 (13), 257.2 (11),

151.0 (10)

HRMS: (ESI+, TOF)

calcd for C22H29Cl2OSi ([M+H]+): 407.1365, found: 407.1368

TLC: major diastereoisomer – Rf 0.22 (99:1 hexane/MTBE) [UV/KMnO4]

minor diastereoisomer – Rf 0.29 (99:1 hexane/MTBE) [UV/KMnO4]

Analysis: C22H28Cl2OSi (407.45)

Calcd: C, 64.85; H, 6.93%

Found: C, 64.86; H, 6.74%

Preparation of tert-Butyl(3,4-dichlorobutoxy)diphenylsilane (29d) (Table 3)




alkene 28d (311 mg, 1.00 mmol, 1.0 equiv) were reacted for 6 h to give a yellow-brown

suspension which, following the work-up described in the general procedure, gave a yellow oil.

Purification via flash column chromatography [62 g high porosity grade SiO2, 34 mm Ø, dry

loaded with 2.2 g SiO2, 100:0 → 99:1 → 98:2 hexane/MTBE (2 L, 500 mL, and 400 mL,

respectively), ca. 10 mL fractions] gave a clear, pale yellow oil (350 mg). Further purification




via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 29d as a clear, colorless,

viscous oil, which solidified to a white solid on standing in a –20 °C freezer for ca. 3 days (346

mg, 91%). The 1H and 13C NMR spectroscopic data matched that for alternative preparations.28

Data for 29d: bp: 163 °C (ABT) (0.05 mm Hg)

mp: 38–40 °C


δ 7.73–7.66 (m, 4 H, HC(2′,2′′)), 7.49–7.38 (m, 6 H, HC(3′,3′′,4′,4′′)), 4.46–4.38 (m,

1 H, HC(3)), 3.95–3.80 (m, 3 H, HC(1,4)), 3.76 (dd, J = 11.4, 6.9 Hz, 1 H, HC(4)),

2.34–2.25 (m, 1 H, HC(2)), 1.87 (app ddt, J = 14.0, 9.0, 4.3 Hz, 1 H, HC(2)), 1.09

(s, 9 H, Sit-Bu) 13C NMR: (126 MHz, CDCl3)

δ 135.54 & 135.51 (C(2′,2′′)), 133.4 & 133.3 (C(1′,1′′)), 129.73 (C(4′,4′′)), 127.7

(C(3′,3′′)), 60.0 (C(1)), 58.0 (C(3)), 48.7 (C(4)), 37.9 (C(2)), 26.8 (SiCMe3), 19.2

(SiCMe3)

IR: (neat)

3071 (w), 3050 (w), 2958 (m), 2931 (m), 2883 (w), 2858 (m), 1589 (w), 1472 (m),

1428 (m), 1390 (w), 1362 (w), 1293 (w), 1267 (w), 1195 (w), 1112 (s), 1091 (m),

998 (w), 941 (w), 823 (m), 757 (w), 738 (m), 701 (s), 688 (w), 664 (w), 614 (m)

MS: (ESI+, TOF)

399.2 (10), 381.1 ([M+H]+, 9), 377.2 (17), 360.2 (20), 359.2 (100), 283.2 (23),

150.0 (15), 149.0 (16), 125.0 (11), 124.1 (57), 111.1 (21)

HRMS: (ESI+, TOF)






Preparation of 4-(3,4-Dichlorobutyl)-2,2-dimethyl-1,3-dioxolane (29e) (Table 3)




alkene 28e (156 mg, 1.00 mmol, 1.0 equiv) were reacted for 4.5 h to give a yellow-brown

suspension which, following the work-up described in the general procedure, gave a 1:1

diastereoisomeric mixture of dichlorides 29e as an orange oil. Purification via flash column

chromatography [45 g SiO2, 34 mm Ø, dry loaded with 1.8 g SiO2, 92:8 hexane/Et2O (700 mL),

ca. 10 mL fractions] gave a colourless oil (205 mg, 1:1 dr). Caution: the product is volatile at ca.

0.05 mm Hg. Further purification via Kugelrohr distillation at reduced pressure (5 mm Hg) gave

29e as a clear, colorless oil (194 mg, 85%, 1:1 dr). An analytically pure sample was obtained by

further purification of an aliquot (180 mg) of 29e via Kugelrohr distillation at reduced pressure

(1 mm Hg) to give a clear, colourless oil (172 mg, 95% mass return).

Data for 29e: bp: 118 °C (ABT) (5 mm Hg) / 90 °C (ABT) (1 mm Hg)

1H NMR: (500 MHz, CDCl3) (N.B. *diastereoisomeric pair)

δ 4.16–4.04 (m, 3 H, HC(3,4′,5′) & HC(3,4′,5′)*), 3.78 (ddd, J = 11.4, 5.1, 3.2 Hz, 1

H, HC(4) & HC(4)*), 3.66 (ddd, J = 11.5, 7.5, 4.1 Hz, 1 H, HC(4) & HC(4)*), 3.55

(app q, J = 7.4 Hz, 1 H, HC(5′) & HC(5′)*), 2.23–2.15 (m, 1 H, HC(2)), 2.11–2.03

(m, 1 H, HC(2)*), 1.92–1.79 (m, 3 H, HC(1,2*)), 1.76–1.63 (m, 3 H, HC(1*,2)),

1.41 (s, 3 H, HC(6′) & HC(6′)*), 1.35 (s, 3 H, HC(7′) & HC(7′)*) 13C NMR: (126 MHz, CDCl3)

δ 109.1 (C(2′)), 109.0 (C(2′)*), 75.6 (C(4′)), 75.0 (C(4′)*), 69.3 (C(5′)), 69.2

(C(5′)*), 61.0 (C(3), 60.7 (C(3)*), 48.1 (C(4)), 48.0 (C(4)*), 31.7 (C(2)), 31.1

(C(2)*), 30.2 (C(1)), 29.8 (C(1)*), 26.9 (C(6′),C(6′)*), 25.64 (C(7′)), 25.59 (C(7′)*)




IR: (neat)

2986 (m), 2937 (w), 2873 (w), 1445 (w), 1380 (m), 1371 (m), 1215 (m), 1154 (m),

1065 (m), 980 (w), 853 (m), 796 (w), 735 (w), 664 (w)

MS: (EI+, TOF)

213.0 (57), 211.0 ([M–CH3]+, 100), 153.0 (13), 151.0 (19), 115.0 (18), 79.1 (41),

72.1 (19)

HRMS: (EI+, TOF)

calcd for C8H13Cl2O2 ([M–CH3]+): 211.0293, found: 211.0294



Calcd: C, 47.59; H, 7.10%

Found: C, 47.44; H, 7.03%

Preparation of 5-(2,3-Dichloropropyl)benzo[d][1,3]dioxole (29f) (Table 3)




safrole 28f (164 mg, 150 µL, 1.01 mmol, 1.0 equiv) were reacted for 3.5 h to give a yellow-

brown suspension which, following the work-up described in the general procedure, gave a

yellow oil. Purification via flash column chromatography [65 g SiO2, 34 mm Ø, dry loaded with

2.0 g SiO2, 100:0 → 99:1 hexane/MTBE (2 L and 1.5 L, respectively), ca. 10 mL fractions then

25 g SiO2, 24 mm Ø, wet loaded, 100:0 → 99:1 hexane/Et2O (both 300 mL), ca. 10 mL

fractions] gave a clear, pale yellow oil (182 mg). Further purification via Kugelrohr distillation at

reduced pressure (0.05 mm Hg) gave 29f as a clear, pale yellow oil (180 mg, 77%).

Data for 29f:

bp: 118 °C (ABT) (0.05 mm Hg)





δ 6.79–6.70 (m, 3 H, HC(3′,4′,6′)), 5.96 (s, 2 H, HC(7′)), 4.23–4.18 (m, 1 H, HC(2)),

3.72 (dd, J = 11.4, 4.7 Hz, 1 H, HC(3)), 3.65 (dd, J = 11.4, 6.9 Hz, 1 H, HC(3)),

3.21 (dd, J = 14.3, 5.7 Hz, 1 H, HC(1)), 2.99 (dd, J = 14.3, 7.1 Hz, 1 H, HC(1)) 13C NMR: (126 MHz, CDCl3)

δ 147.7 (C(1′)), 146.7 (C(2′)), 129.8 (C(5′)), 122.7 (C(4′)), 109.8 (C(6′)), 108.3

(C(3′)), 101.0 (C(7′)), 61.0 (C(2)), 47.3 (C(3)), 40.6 (C(1))

IR: (neat)

2895 (w), 2778 (w), 1852 (w), 1608 (w), 1504 (m), 1490 (m), 1444 (m), 1364 (w),

1250 (m), 1191 (m), 1123 (w), 1100 (w), 1039 (m), 992 (w), 930 (m), 879 (m), 810

(w), 776 (w), 724 (w), 669 (w), 601 (w)

MS: (EI+, TOF)

234.0 (11), 232.0 (M+, 18), 135.0 ([M–C2H3Cl2]+, 100), 77.0 (10)

HRMS: (EI+, TOF)

calcd for C10H10Cl2O2 (M+): 232.0058, found: 232.0057



Calcd: C, 51.53; H, 4.32%

Found: C, 51.71; H, 4.22%

Preparation of (l)-4,5-Dichlorooctane (29g) (Table 3)




Me3SiCl (445 mg, 520 µL, 4.10 mmol, 2.0 equiv), and (E)-4-octene 28g (229 mg, 320 µL, 2.04

mmol, 1.0 equiv) were reacted for 4 h to give an orange-red solution which, following the work-




up described in the general procedure, gave an orange oil (99:1 dr). Caution: the product is

highly volatile and should not be left on the rotary evaporator for an extended period.


loaded, petroleum ether (500 mL), ca. 10 mL fractions] gave a yellow oil (249 mg, ≥90% purity)

(N.B. solvent was removed in vacuo at 5–8 °C, ca. 20 mm Hg). Further purification via

Kugelrohr distillation at reduced pressure (20 mm Hg) gave 29g as a clear, colorless oil (151 mg,

40%, contaminated with 3% vinylic chloride by-product). A yellow residue (79.0 mg) containing

29g (≥90%) and an inseparable, unidentified selenium-containing by-product remained, which

was not purified further.

Data for 29g: bp: 120 °C (ABT) (20 mm Hg)


δ 4.07–4.04 (m, 2 H, HC(4,5)), 1.92–1.84 (m, 2 H, HC(3,6)), 1.83–1.75 (m, 2 H,

HC(3,6)), 1.66–1.55 (m, 2 H, HC(2,7)), 1.47–1.36 (m, 2 H, HC(2,7)), 0.95 (t, J =

7.4 Hz, 6 H, HC(1,8)) 13C NMR: (126 MHz, CDCl3)

δ 65.3 (C(4,5)), 36.4 (C(3,6)), 19.9 (C(2,7)), 13.5 (C(1,8))

IR: (neat)

2962 (s), 2935 (m), 2875 (m), 1466 (m), 1461 (m), 1433 (w), 1382 (w), 1274 (w),

1257 (w), 1206 (w), 1122(w), 1049 (w), 985(w), 876 (w), 764 (w), 751 (m), 721

(w), 647(m)

MS: (EI+, TOF)

182.1 (M+, 5), 148.1 (22), 146.1 ([M–Cl]+, 65), 111.1 ([M–2Cl]+, 88), 110.1 (58),

55.1 (100)

HRMS: (EI+, TOF)

calcd for C8H16Cl2 (M+): 182.0629, found: 182.0628






Preparation of (l)-{[(4,5-Dichlorohexyl)oxy]methyl}benzene (18) (Table 3)




alkene 17 (191 mg, 1.00 mmol, 1.0 equiv) were reacted for 3.5 h to give a yellow-brown

suspension which, following the work-up described in the general procedure, gave a yellow oil

(99:1 dr). Purification via flash column chromatography [69 g SiO2, 34 mm Ø, dry loaded with

1.9 g SiO2, 98:2 hexane/Et2O (1.1 L), ca. 10 mL fractions] gave a pale yellow oil (190 mg).

Further purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 18 as a

clear, colorless oil (185 mg, 71%).

Data for 18: bp: 118 °C (ABT) (0.05 mm Hg)


δ 7.38–7.27 (m, 5 H, HC(2′,3′,4′)), 4.53 & 4.51 (ABq, JAB = 12.0 Hz, 2 H, HC(5′)),

4.26 (qd, J = 6.7, 3.0 Hz, 1 H, HC(5)), 4.04 (dt, J = 9.9, 3.2 Hz, 1 H, HC(4)), 3.57–

3.49 (m, 2 H, HC(1)), 2.13–2.05 (m, 1 H, HC(3)), 1.96–1.80 (m, 2 H, HC(2,3)),

1.77–1.69 (m, 1 H, HC(2)), 1.58 (d, J = 6.7 Hz, 3 H, HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 138.3 (C(1′)), 128.4 (C(3′)), 127.63 (C(2′)), 127.59 (C(4′)), 72.9 (C(5′)), 69.4

(C(1)), 66.1 (C(4)), 60.0 (C(5)), 30.9 (C(3)), 26.9 (C(2)), 20.8 (C(6))

IR: (neat)

3399 (w), 3030 (w), 2928 (m), 2857 (m), 2795 (w), 1496 (w), 1453 (m), 1381 (w),

1362 (w), 1104 (s), 1028 (m), 996 (w), 913 (w), 737 (m), 698 (m), 615 (m)

MS: (ESI+, TOF)

437.2 (23), 415.2 (38), 413.3 (13), 381.3 (25), 359.2 (27), 341.3 (20), 284.3 (43),

282.3 (74), 263.1 (31), 261.1 ([M+H]+, 40), 256.3 (45), 229.2 (61), 189.1 (27),

185.1 (49), 124.1 ([(M–CH2OCH2Ph)-CH3]+, 93), 91.1 ([CH2Ph]+, 100)




HRMS: (ESI+, TOF)

calcd for C13H19Cl2O ([M+H]+): 261.0813, found: 261.0826


Analysis: C13H18Cl2O (261.19)

Calcd: C, 59.78; H, 6.95%

Found: C, 60.06; H, 6.84%

Preparation of (u)-{[(4,5-Dichlorohexyl)oxy]methyl}benzene (29h) (Table 3)




alkene 28h (191 mg, 1.00 mmol, 1.0 equiv) were reacted for 4 h to give a yellow-brown


(>99:1 dr). Purification via flash column chromatography [75 g SiO2, 34 mm Ø, dry loaded with

2.2 g SiO2, 99:1 hexane/EtOAc (1.5 L), ca. 10 mL fractions], followed by further purification of

the mixed fractions [52 g high porosity grade SiO2, 34 mm Ø, dry loaded with 1.8 g SiO2,

98.4:1.6 hexane/MTBE (1 L), ca. 10 mL fractions], gave a pale yellow oil (176 mg). Further

purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 29h as a clear,

colorless oil (175 mg, 67%).

Data for 29h: bp: 118 °C (ABT) (0.05 mm Hg)



4.11 (app pent, J = 6.5 Hz, 1 H, HC(5)), 3.98 (ddd, J = 9.5, 6.4, 2.9 Hz, 1 H, HC(4)),

3.56–3.48 (m, 2 H, HC(1)), 2.18–2.12 (m, 1 H, HC(3)), 1.98–1.90 (m, 1 H, HC(2)),

1.85–1.70 (m, 2 H, HC(2,3)), 1.62 (d, J = 6.6 Hz, 3 H, HC(6))





δ 138.4 (C(1′)), 128.4 (C(3′)), 127.62 (C(2′)), 127.58 (C(4′)), 72.9 (C(5′)), 69.3

(C(1)), 67.1 (C(4)), 60.2 (C(5)), 31.9 (C(3)), 26.5 (C(2)), 21.9 (C(6))

IR: (neat)

3087 (w), 3064 (w), 3031 (w), 2983 (w), 2935 (m), 2858 (m), 2795 (w), 1496 (w),

1454 (m), 1380 (w), 1362 (w), 1309 (w), 1244 (w), 1198 (m), 1106 (s), 1028 (w),

996 (w), 911 (w), 737 (m), 698 (m), 648 (m), 615 (m)

MS: (ESI+, TOF)

359.2 (27), 283.2 ([M+Na]+, 15), 263.1 (17), 261.1 ([M+H]+, 26), 125.1 (21), 124.2

(45), 124.1 ([(M–CH2OCH2Ph)-CH3]+, 100), 107.1 ([OCH2Ph]+, 12), 91.1

([CH2Ph]+, 53)

HRMS: (ESI+, TOF)




Calcd: C, 59.78; H, 6.95%

Found: C, 59.98; H, 6.73%

Preparation of tert-Butyl{[(l)-4,5-dichlorohexyl]oxy}diphenylsilane (14) (Table 3)




alkene 13 (339 mg, 1.00 mmol, 1.0 equiv) were reacted for 4 h to give an orange-red solution

which, following the work-up described in the general procedure, gave an orange oil (>99:1 dr).


loaded with 1.8 g SiO2, 99:1 → 98:2 → 96:4 → 95:5 petroleum ether/benzene (1.5 L, 500 mL,




200 mL, and 200 mL, respectively), ca. 10 mL fractions then 26 g SiO2, 24 mm Ø, wet loaded,

100:0 → 99.2:0.8 hexane/Et2O (400 mL and 500 mL, respectively), ca. 10 mL fractions] gave a

clear, colourless oil (266 mg). Further purification via Kugelrohr distillation at reduced pressure

(0.05 mm Hg) gave 14 as a clear, colorless oil (262 mg, 64%).

Data for 14: bp: 171 °C (ABT) (0.05 mm Hg)


δ 7.69–7.66 (m, 4 H, HC(2′,2′′)), 7.46–7.37 (m, 6 H, HC(3′,3′′,4′,4′′)), 4.24 (qd, J =

6.6, 3.1 Hz, 1 H, HC(5)), 4.04 (dt, J = 9.6, 3.4 Hz, 1 H, HC(4)), 3.76–3.68 (m, 2 H,

HC(1)), 2.15–2.07 (m, 1 H, HC(3)), 1.88–1.78 (m, 2 H, HC(2,3)), 1.71–1.62 (m, 1

H, HC(2)), 1.57 (d, J = 6.7 Hz, 3 H, HC(6)), 1.07 (s, 9 H, Sit-Bu) 13C NMR: (126 MHz, CDCl3)

δ 135.6 (C(2′,2′′)), 133.79 & 133.76 (C(1′,1′′)), 129.6 (C(4′,4′′)), 127.7 (C(3′,3′′)),

66.1 (C(4)), 63.1 (C(1)), 60.0 (C(5)), 30.5 (C(3)), 29.5 (C(2)), 26.9 (SiCMe3), 20.8

(C(6)), 19.2 (SiCMe3)

IR: (neat)

3071 (w), 3050 (w), 2998 (w), 2958 (m), 2931 (m), 2895 (w), 2858 (m), 2740 (w),

1590 (w), 1472 (m), 1463 (w), 1445 (w), 1428 (m), 1389 (w), 1361 (w), 1261 (w),

1232 (w), 1111 (s), 1007 (w), 997 (w), 970 (w), 823 (m), 737 (m), 702 (m), 647 (w),

614 (m)

MS: (ESI+, TOF)

411.1 (26), 409.2 ([M+H]+, 36), 257.1 (48), 179.1 (14), 155.0 (60), 153.0 (92),

134.1 (100), 117.0 (38)

HRMS: (ESI+, TOF)






Preparation of tert-Butyl{[(u)-4,5-dichlorohexyl]oxy}diphenylsilane (29i) (Table 3)




alkene 28i (340 mg, 1.00 mmol, 1.0 equiv) were reacted for 6 h to give a yellow-green



2.8 g SiO2, 99:1 hexane/MTBE (1.5 L), ca. 10 mL fractions] gave a pale yellow oil (≥85%

purity). Following division into two batches, further purification of each batch via flash column

chromatography {[batch I (156 mg): 42 g high porosity grade SiO2, 34 mm Ø, dry loaded with

1.8 g SiO2, 100:0 → 99:1 hexane/MTBE (2.5 L and 1.5 L, respectively), ca. 10 mL fractions]

and [batch II (176 mg): 46 g high porosity grade SiO2, 34 mm Ø, dry loaded with 2.0 g SiO2,

100:0 → 99:1 hexane/MTBE (2.5 L and 1.5 L, respectively), ca. 10 mL fractions]} gave a clear,

pale yellow oil (281 mg). Further purification via Kugelrohr distillation at reduced pressure (0.05

mm Hg) gave 29i as a clear, colorless oil (274 mg, 67%).

Data for 29i: bp: 171 °C (ABT) (0.05 mm Hg)


δ 7.69–7.65 (m, 4 H, HC(2′,2′′)), 7.46–7.37 (m, 6 H, HC(3′,3′′,4′,4′′)), 4.10 (app

pent, J = 6.5 Hz, 1 H, HC(5)), 3.99 (ddd, J = 9.4, 6.5, 3.0 Hz, 1 H, HC(4)), 3.75–

3.67 (m, 2 H, HC(1)), 2.21–2.14 (m, 1 H, HC(3)), 1.90–1.76 (m, 2 H, HC(2,3)),

1.72–1.65 (m, 1 H, HC(2)), 1.62 (d, J = 6.5 Hz, 3 H, HC(6)), 1.06 (s, 9 H, Sit-Bu) 13C NMR: (126 MHz, CDCl3)

δ 135.6 (C(2′,2′′)), 133.76 & 133.74 (C(1′,1′′)), 129.6 (C(4′,4′′)), 127.7 (C(3′,3′′)),

67.2 (C(4)), 63.0 (C(1)), 60.2 (C(5)), 31.7 (C(3)), 29.1 (C(2)), 26.8 (SiCMe3), 21.9

(C(6)), 19.2 (SiCMe3)




IR: (neat)

3071 (w), 3050 (w), 2958 (m), 2931 (m), 2895 (w), 2858 (m), 2740 (w), 1590 (w),

1473 (w), 1463 (w), 1446 (w), 1428 (m), 1381 (w), 1361 (w), 1246 (w), 1195 (w),

1111 (s), 1007 (w), 998 (w), 969 (w), 823 (m), 737 (w), 702 (s), 688 (w), 650 (m),

614 (m)

MS: (ESI+, TOF)

415.3 (14), 409.2 ([M+H]+, 3), 359.2 (10), 310.3 (20), 284.3 (29), 283.3

([CH2CH2OSiPh2t-Bu]+, 23), 282.3 (100), 256.3 ([HOSiPh2t-Bu]+, 23)

HRMS: (ESI+, TOF)




Calcd: C, 64.53; H, 7.39%

Found: C, 64.68; H, 7.61%

Preparation of {[(l)-4,5-Dichloro-7-phenylheptyl]oxy}tri-iso-propylsilane (29j) and (l)-4,5-

Dichloro-7-phenylheptan-1-ol (S23) (Table 3)




alkene 28j (347 mg, 1.00 mmol, 1.0 equiv) were reacted for 5 h to give a yellow-green


(97:3 dr w.r.t. 29j). Partial cleavage of the tri-iso-propylsilyl group was observed; however, the




ratio of 29j to the free alcohol dichloride S23 could not be determined by 1H NMR spectroscopy

of the crude mixture. Purification via flash column chromatography [73 g high porosity grade

SiO2, 34 mm Ø, dry loaded with 2.5 g SiO2, 100:0 → 99:1 hexane/Et2O followed by 75:25 →

60:40 hexane/EtOAc (2 L, 800 mL, 500 mL, and 400 mL, respectively), ca. 10 mL fractions]

gave 29j and S23 as pale yellow oils. Further purification of the mixed fractions, containing 29j,

[63 g high porosity grade SiO2, 34 mm Ø, dry loaded with 2.5 g SiO2, 100:0 → 99:1

hexane/MTBE (3.5 L and 1 L, respectively), ca. 10 mL fractions] gave a clear, pale yellow oil

(163 mg). Further purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave

29j as a clear, pale yellow oil (156 mg, 37%, contaminated with ~2% of tentatively assigned

cyclized by-products). Further purification of S23 [16 g SiO2, 18 mm Ø, wet loaded with CH2Cl2,


clear, colourless oil (68.8 mg). Further purification via Kugelrohr distillation at reduced pressure

(0.05 mm Hg) gave S23 (64.9 mg, 24%) as a clear, colourless oil.

Data for 29j: bp: 163 °C (ABT) (0.05 mm Hg)


δ 7.34–7.28 (m, 2 H, HC(2′)), 7.24–7.18 (m, 3 H, HC(3′,4′)), 4.12 (dt, J = 9.8, 3.6

Hz, 1 H, HC(4)), 4.02 (dt, J = 9.7, 3.3 Hz, 1 H, HC(5)), 3.77–3.67 (m, 2 H, HC(1)),

2.93 (ddd, J = 13.8, 8.6, 5.2 Hz, 1 H, HC(7)), 2.74 (dt, J = 13.9, 8.2 Hz, 1 H,

HC(7)), 2.25–2.11 (m, 2 H, HC(6)), 2.11–2.02 (m, 1 H, HC(3)), 1.87 (dtd, J = 14.3,

9.7, 4.8 Hz, 1 H, HC(3)), 1.82–1.74 (m, 1 H, HC(2)), 1.67–1.58 (m, 1 H, HC(2)),

1.14–0.99 (m, 21 H, Sii-Pr3) 13C NMR: (126 MHz, CDCl3)

δ 140.5 (C(1′)), 128.53 (C(2′)), 128.50 (C(3′)), 126.2 (C(4′)), 65.5 (C(4)), 64.6

(C(5)), 62.6 (C(1)), 36.2 (C(6)), 32.7 (C(7)), 31.4 (C(3)), 29.9 (C(2)), 18.0

(SiCH(CH3)2), 12.0 (SiCH(CH3)2)

IR: (neat)

3064 (w), 3028 (w), 2943 (m), 2866 (m), 2727 (w), 1604 (w), 1497 (w), 1463 (m),

1383 (w), 1366 (w), 1235 (w), 1108 (s), 1013 (w), 996 (m), 919 (w), 882 (m), 789

(w), 732 (w), 699 (m), 681 (m), 615 (m)




MS: (ESI+, TOF)

417.2 ([M+H]+, 11), 391.3 (13), 390.4 (33), 389.3 (94), 230.2 (23), 229.2 ([M–

CH2OSii-Pr3]+, 100), 215.0 (21), 207.1 (53)

HRMS: (ESI+, TOF)



Data for S23: bp: 150 °C (ABT) (0.05 mm Hg)


δ 7.34–7.28 (m, 2 H, HC(2′)), 7.24–7.19 (m, 3 H, HC(3′,4′)), 4.08 (dt, J = 10.0, 3.1

Hz, 1 H, HC(4)), 4.02 (dt, J = 9.9, 3.2 Hz, 1 H, HC(5)), 3.69 (tt, J = 6.0, 3.3 Hz, 2

H, HC(1)), 2.93 (ddd, J = 13.8, 8.6, 5.1 Hz, 1 H, HC(7)), 2.73 (dt, J = 13.8, 8.2 Hz,

1 H, HC(7)), 2.26–2.11 (m, 2 H, HC(6)), 2.08–2.00 (m, 1 H, HC(3)), 1.92–1.78 (m,

2 H, HC(2,3)), 1.69–1.59 (m, 1 H, HC(2)), 1.38 (br s, 1 H, OH) 13C NMR: (126 MHz, CDCl3)

δ 140.4 (C(1′)), 128.54 (C(2′)), 128.50 (C(3′)), 126.2 (C(4′)), 65.4 (C(4)), 64.5

(C(5)), 62.1 (C(1)), 36.0 (C(6)), 32.6 (C(7)), 31.1 (C(3)), 29.7 (C(2))

IR: (neat)

3577 (m), 3355 (w), 3086 (w), 3063 (w), 3027 (w), 2954 (m), 2867 (w), 1950 (w),

1873 (w), 1809 (w), 1603 (w), 1583 (w), 1497 (m), 1455 (m), 1436 (w), 1377 (w),

1288 (w), 1261 (w), 1232 (w), 1057 (m), 1030 (w), 939 (w), 909 (w), 849 (w), 751

(m), 700 (s), 648 (w), 600 (w)

MS: (ESI+, TOF)

263.1 (12), 261.1 ([M+H]+, 18), 209.1 (16), 207.1 ([M–H2O–Cl]+, 51), 189.1 ([M–

2Cl]+, 47), 173.0 (38), 171.1 (44), 171.0 ([M–2Cl–H2O]+, 100)

HRMS: (ESI+, TOF)






Preparation of Ethyl (l)-4,5-Dichlorohexanoate (29k) (Table 3)




alkene 28k (143 mg, 1.01 mmol, 1.0 equiv) were reacted for 3.5 h to give a yellow-brown

suspension which, following the work-up described in the general procedure, gave an orange oil


2.4 g SiO2, 96:4 hexane/MTBE (1 L), ca. 10 mL fractions], followed by further purification of

the mixed fractions [24 g SiO2, 24 mm Ø, dry loaded with 1.6 g SiO2, 96:4 hexane/MTBE (500

mL), ca. 10 mL fractions], gave a pale yellow oil (176 mg). Further purification via flash column

chromatography [27 g SiO2, 24 mm Ø, wet loaded, 98:2 hexane/Et2O (600 mL), ca. 10 mL

fractions] gave a colourless oil (158 mg). Caution: the product is volatile at ca. 0.05 mm Hg.

Further purification via Kugelrohr distillation at reduced pressure (5 mm Hg) gave 29k as a clear,


Data for 29k: bp: 118 °C (ABT) (5 mm Hg)


δ 4.26 (qd, J = 6.7, 3.0 Hz, 1 H, HC(5)), 4.14 (q, J = 7.2 Hz, 2 H, CO2CH2CH3),

4.10 (dt, J = 10.7, 3.0 Hz, 1 H, HC(4)), 2.59 (ddd, J = 16.7, 7.8, 5.6 Hz, 1 H,

HC(2)), 2.54–2.45 (m, 1 H, HC(2)), 2.28 (dtd, J = 14.9, 7.8, 2.9 Hz, 1 H, HC(3)),

2.10–1.97 (m, 1 H, HC(3)), 1.59 (d, J = 6.7 Hz, 3 H, HC(6)), 1.26 (t, J = 7.1 Hz, 3

H, CO2CH2CH3) 13C NMR: (126 MHz, CDCl3)

δ 172.6 (C(1)), 65.1 (C(4)), 60.6 (CO2CH2CH3), 59.8 (C(5)), 31.1 (C(2)), 29.2

(C(3)), 20.8 (C(6)), 14.2 (CO2CH2CH3)

IR: (neat)

2983 (m), 2936 (w), 1734 (s), 1443 (m), 1378 (m), 1352 (w), 1325 (w), 1300 (w),




1267 (m), 1187 (m), 1099 (m), 1032 (m), 994 (w), 908 (w), 857 (w), 804 (w), 691

(w), 649 (w), 603 (w)

MS: (ESI+, TOF)

284.3 (25), 282.3 (16), 256.3 (21), 252.2 (13), 215.1 (41), 213.1 ([M+H]+, 57),

181.1 (11), 179.1 (19), 177.1 ([M–Cl]+, 53), 150.0 (14), 149.0 (40), 141.1 ([M–

2Cl]+, 100), 131.0 (23), 119.1 (16), 113.1 (68), 99.1 (37)

HRMS: (ESI+, TOF)

calcd for C8H15Cl2O2 ([M+H]+): 213.0449, found: 213.0457



Calcd: C, 45.09; H, 6.62%

Found: C, 44.96; H, 6.38%

Preparation of (l)-4,5-Dichlorohexyl Cyclopropanecarboxylate (29l) (Table 3)




alkene 28l (169 mg, 1.00 mmol, 1.0 equiv) were reacted for 3.5 h to give a yellow-brown



2.2 g SiO2, 97:3 hexane/EtOAc (1 L), ca. 10 mL fractions] gave a pale yellow oil (174 mg).

Caution: the product is volatile at ca. 0.05 mm Hg. Further purification via Kugelrohr distillation

at reduced pressure (0.05 mm Hg) gave 29l as a clear, colorless oil (166 mg, 69%).

Data for 29l: bp: 81 °C (ABT) (0.05 mm Hg)





δ 4.26 (qd, J = 6.7, 3.0 Hz, 1 H, HC(5)), 4.17–4.07 (m, 2 H, HC(1)), 4.03 (dt, J =

10.1, 3.1 Hz, 1 H, HC(4)), 2.08–2.00 (m, 1 H, HC(3)), 2.00–1.91 (m, 1 H, HC(2)),

1.87–1.80 (m, 1 H, HC(3)), 1.80–1.71 (m, 1 H, HC(2)), 1.64–1.57 (m, 1 H, HC(8)),

1.59 (d, J = 6.7 Hz, 3 H. HC(6)), 1.01–0.97 (m, 2 H, HC(9,10)), 0.86 (dq, J = 7.6,

3.9 Hz, 2 H, HC(9,10)) 13C NMR: (126 MHz, CDCl3)

δ 174.8 (C(7)), 65.5 (C(4)), 63.5 (C(1)), 59.8 (C(5)), 30.3 (C(3)), 26.0 (C(2)), 20.6

(C(6)), 12.8 (C(8)), 8.4 (C(9,10)

IR: (neat)

3099 (w), 3016 (w), 2961 (m), 1727 (s), 1447 (m), 1404 (m), 1378 (m), 1365 (m),

1269 (m), 1235 (w), 1200 (m), 1175 (s), 1100 (w), 1077 (m), 1032 (w), 986 (w),

953 (w), 915 (w), 898 (w), 852 (w), 824 (w), 771 (w), 747 (w), 695 (w), 650 (w),

613 (w)

MS: (ESI+, TOF)

415.3 (23), 381.3 (18), 310.3 (18), 304.3 (13), 284.3 (29), 283.3 (24), 282.3 (100),

263.1 (19), 261.1 (19), 256.3 (26), 254.0 (55), 252.0 (31), 239.1 ([M+H]+, 23),

229.2 (26), 185.1 (15), 155.0 (29), 153.0 ([M–CO2CH(CH2)2]+, 43), 124.1 (30),

117.1 (15)

HRMS: (ESI+, TOF)




Calcd: C, 50.23; H, 6.74%

Found: C, 50.39; H, 6.70%




Preparation of 2-Benzyl-2-[(l)-3,4-dichloropentyl]-1,3-dioxolane (29m) (Table 3)




alkene 28m (233 mg, 1.00 mmol, 1.0 equiv) were reacted for 3.5 h to give a yellow-brown



2.2 g SiO2, 97:3 hexane/EtOAc (1.2 L), ca. 10 mL fractions] gave a pale yellow oil (226 mg).

Further purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 29m as a

clear, pale yellow oil (222 mg, 73%).

Data for 29m: bp: 150 °C (ABT) (0.05 mm Hg)


δ 7.31–7.21 (m, 5 H, HC(2′,3′4′)), 4.23 (qd, J = 6.7, 3.0 Hz, 1 H, HC(6)), 4.02 (dt, J

= 9.9, 3.2 Hz, 1 H, HC(5)), 3.93–3.85 (m, 2 H, HC(8,9)), 3.77–3.68 (m, 2 H,

HC(8,9)), 2.93 & 2.89 (ABq, JAB = 13.8 Hz, 2 H, HC(1)), 2.13–2.04 (m, 1 H,

HC(4)), 1.94 (ddd, J = 14.6, 10.2, 4.6 Hz, 1 H, HC(3)), 1.90–1.81 (m, 1 H, HC(4)),

1.70 (ddd, J = 13.5, 10.3, 5.3 Hz, 1 H, HC(3)), 1.57 (d, J = 6.7 Hz, 3 H, HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 136.4 (C(1′)), 130.5 (C(3′)), 128.0 (C(2′)), 126.5 (C(4′)), 110.8 (C(2)), 66.2 (C(5)),

65.3 & 65.2 (C(8,9), 59.9 (C(6)), 43.9 (C(1)), 34.6 (C(3)), 27.9 (C(4)), 20.6 (C(7))

IR: (neat)

3086 (w), 3062 (w), 3030 (w), 2957 (m), 2928 (m), 2886 (m), 1605 (w), 1496 (m),

1477 (m), 1455 (m), 1446 (m), 1380 (w), 1315 (w), 1266 (m), 1228 (m), 1197 (m),

1129 (m), 1078 (w), 1037 (m), 983 (w), 949 (m), 932 (w), 853 (w), 829 (w), 751

(m), 702 (m), 648 (m)




MS: (ESI+, TOF)

305.1 (62), 304.1 (16), 303.1 ([M+H]+, 100), 261.1 (37), 259.1 (63), 225.1 ([M–

Ph]+, 13), 223.1 (46), 219.2 (35), 183.1 (12), 124.1 (20), 105.1 (10)

HRMS: (ESI+, TOF)




Calcd: C, 59.42; H, 6.65%

Found: C, 59.66; H, 6.65%

Preparation of Methyl (l)-(E)-6,7-Dichlorooct-2-enoate (29n) (Table 3)




alkene 28n (154 mg, 1.00 mmol, 1.0 equiv) were reacted for 4.5 h to give a yellow-brown


(99:1 dr). Purification via flash column chromatography {[74 g SiO2, 34 mm Ø, dry loaded with

2.5 g SiO2, 96:4 hexane/EtOAc (1.2 L), ca. 10 mL fractions] then [26 g SiO2, 24 mm Ø, wet

loaded with hexane, 96:4 hexane/EtOAc (500 mL), ca. 10 mL fractions]} gave a colourless oil

(162 mg). Caution: the product is volatile at ca. 0.05 mm Hg. Further purification via Kugelrohr

distillation at reduced pressure (5 mm Hg) gave 29n as a clear, colourless oil (158 mg, 70%).

Data for 29n: bp: 140 °C (ABT) (5 mm Hg)


δ 6.93 (ddd, J = 15.6, 7.6, 6.4 Hz, 1 H, HC(3)), 5.90 (dt, J = 15.7, 1.5 Hz, 1 H,

HC(2)), 4.24 (qd, J = 6.7, 3.0 Hz, 1 H, HC(7)), 3.98 (dt, J = 10.6, 3.0 Hz, 1 H,

HC(6)), 3.73 (s, 3 H, CO2CH3), 2.56–2.47 (m, 1 H, HC(4)), 2.40–2.31 (m, 1 H,




HC(4)), 2.12–2.04 (m, 1 H, HC(5)), 1.98–1.88 (m, 1 H, HC(5)), 1.58 (d, J = 6.7 Hz,

3 H, HC(8)) 13C NMR: (126 MHz, CDCl3)

δ 166.7 (C(1)), 147.0 (C(3)), 122.2 (C(2)), 64.8 (C(6)), 59.7 (C(7)), 51.5 (CO2CH3),

31.9 (C(5)), 29.1 (C(4)), 20.5 (C8))

IR: (neat)

2985 (w), 2952 (m), 2847 (w), 1726 (s), 1660 (m), 1436 (m), 1381 (w), 1327 (w),

1314 (w), 1273 (m), 1231 (w), 1202 (m), 1161 (m), 1105 (w), 1078 (w), 1040 (w),

989 (w), 914 (w), 856 (w), 822 (w), 792 (w), 721 (w), 698 (w), 650 (w), 614 (w)

MS: (ESI+, TOF)

421.3 (38), 399.3 (29), 365.1 (13), 363.1 (19), 338.4 (14), 327.2 (21), 313.2 (38),

311.2 (92), 310.3 (18), 293.0 (23), 291.2 (27), 291.0 (31), 289.2 (61), 282.3 (100),

280.3 (15), 259.2 (21), 257.2 (45), 256.3 (25), 229.2 (30), 227.1 (54), 225.1

([M+H]+, 75), 185.1 (17), 93.1 (29)

HRMS: (ESI+, TOF)




Calcd: C, 48.02; H, 6.27%

Found: C, 48.26; H, 6.02%

Preparation of tert-Butyl Benzyl[(u)-4,5-dichlorohexyl]carbamate (29o) (Table 3)




alkene 28o (290 mg, 1.00 mmol, 1.0 equiv) were reacted for 5 h to give a yellow-brown






2.5 g SiO2, 97:3 → 96:4 hexane/EtOAc (1.2 L and 300 mL, respectively), ca. 10 mL fractions],

followed by further purification of the mixed fractions [45 g SiO2, 30 mm Ø, dry loaded with 1.5

g SiO2, 97:3 hexane/EtOAc (1 L), ca. 10 mL fractions], gave a pale yellow oil (275 mg). Further

purification via flash column chromatography [27 g SiO2, 24 mm Ø, wet loaded, 96:4

hexane/EtOAc (500 mL), ca. 10 mL fractions] gave a clear, colourless oil (263 mg). Further

purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 29o as a clear,


Data for 29o: bp: 158 °C (ABT) (0.05 mm Hg)

1H NMR: (500 MHz, MeCN-d3, VT at 53 °C, calibrated with ethylene glycol)

δ 7.39–7.34 (m, 2 H, HC(2′)), 7.33–7.27 (m, 3 H, HC(3′,4′)), 4.49 & 4.43 (ABq,

JAB = 15.7 Hz, 2 H, HC(5′)), 4.25 (qd, J = 6.5, 5.2 Hz, 1 H, HC(5)), 4.10 (dt, J =

9.1, 3.9 Hz, 1 H, HC(4)), 3.34–3.22 (m, 2 H, HC(1)), 1.97–1.89 (m, 1 H, HC(3)),

1.87–1.78 (m, 1 H, HC(3)), 1.77–1.61 (m, 2 H, HC(2)), 1.58 (d, J = 6.6 Hz, 3 H,

HC(6)), 1.50 (s, 9 H, Ot-Bu) 13C NMR: (126 MHz, MeCN-d3, VT at 53 °C, calibrated with ethylene glycol)

δ 156.6 (NCO2t-Bu), 140.1 (C(1′)), 129.5 (C(3′)), 128.5 (C(4′)), 128.1 (C(2′)), 80.3

(NCO2CMe3), 68.4 (C(4)), 61.6 (C(5)), 51.2 (C(5′)), 47.0 (C(1)), 32.9 (C(3)), 28.92

& 28.90 (NCO2CMe3), 26.0 (C(2)), 21.84 & 21.81 (C(6))

IR: (neat)

3088 (w), 3065 (w), 3030 (w), 2977 (m), 2934 (m), 1694 (s), 1605 (w), 1586 (w),

1496 (w), 1465 (m), 1454 (m), 1416 (m), 1391 (w), 1381 (w), 1366 (m), 1308 (w),

1245 (m), 1166 (m), 1137 (m), 1176 (w), 1029 (w), 1002 (w), 969 (w), 880 (w),

769 (w), 737 (w), 700 (m), 650 (w)

MS: (ESI+, TOF)

382.2 ([M+Na]+, 11), 362.2 (13), 360.2 ([M+H]+, 21), 308.1 (14), 306.1 (72), 305.1

(18), 304.1 (100), 164.1 (12)

HRMS: (ESI+, TOF)

calcd for C18H28Cl2NO2 ([M+H]+): 360.1497, found: 360.1503





Analysis: C18H27Cl2NO2 (360.32)

Calcd: C, 60.00; H, 7.55%

Found: C, 59.96; H, 7.72%

Preparation of 2-[(u)-4,5-Dichlorohexyl]isoindoline-1,3-dione (29p) (Table 3)




alkene 28p (231 mg, 1.01 mmol, 1.0 equiv) were reacted for 3.5 h to give a yellow-brown



2.2 g SiO2, 92:8 → 90:10 hexane/EtOAc (1.2 L and 100 mL, respectively), ca. 10 mL fractions]

gave a pale yellow oil, which solidified on standing in a –20 °C freezer for ca. 1 day (239 mg).

Further purification was performed via recrystallization from boiling Et2O (2 mL), with gradual

cooling to rt and, finally, to 0 °C in a 20 mL scintillation vial loosely sealed with a screw top cap.

The crystals were collected via filtration through filter paper in a Hirsch funnel under house

vacuum, washed with (–78 °C) pentane (3 × ca. 1 mL), crushed with a spatula, and dried in

vacuo (0.05 mm Hg) overnight to give an off-white crystalline solid (138 mg). The filtrate was

concentrated in vacuo (20–23 °C, ca. 20 mm Hg) and the pale yellow solid recovered (102 mg)

was re-subjected to the same recrystallization conditions. The material from both crops was

combined to give 29p as an off-white crystalline solid (217 mg, 72%, >97:3 dr).

Data for 29p: mp: 64–65 °C (Et2O)


δ 7.87–7.82 (m, 2 H, HC(3′)), 7.75–7.69 (m, 2 H, HC(4′)), 4.07 (app pent, J = 6.5

Hz, 1 H, HC(5)), 4.02–3.95 (m, 1 H, HC(4)), 3.73 (t, J = 5.9 Hz, 2 H, HC(1)), 2.08–




1.96 (m, 2 H, HC(2,3)), 1.88–1.77 (m, 2 H, HC(2,3)), 1.60 (d, J = 5.9 Hz, 3 H,

HC(6))


δ 168.3 (C(1′)), 134.0 (C(4′)), 132.0 (C(2′)), 123.3 (C(3′)), 66.3 (C(4)), 60.0 (C(5)),

37.1 (C(1)), 32.1 (C(3)), 25.4 (C(2)), 22.0 (C(6))

IR: (neat)

2935 (w), 2873(w), 1771 (m), 1716 (s), 1615 (w), 1465 (w), 1456 (w), 1436 (w),

1397 (m), 1366 (w), 1331 (w), 1257 (w), 1220 (w), 1203 (w), 1186 (w), 1088 (w),

1061 (w), 1045 (w), 1021 (m), 988 (w), 887 (w), 835 (w), 801 (w), 750 (w), 720

(m), 713 (m), 648 (m),

MS: (ESI+, TOF)

304.1 (14), 302.1 (72), 300.1 ([M+H]+, 100), 282.3 (12), 264.1 ([M–Cl]+, 19), 228.1

([M–2Cl]+, 36), 160.1 ([C9H6NO2]+, 13)

HRMS: (ESI+, TOF)

calcd for C14H16Cl2NO2 ([M+H]+): 300.0558, found: 300.0558


Analysis: C14H15Cl2NO2 (300.18)

Calcd: C, 56.02; H, 5.04%

Found: C, 56.13; H, 4.97%

Preparation of tert-Butyl{[(l)-2,3-dichlorohexyl]oxy}diphenylsilane (29q) (Table 3)




alkene 28q (340 mg, 1.00 mmol, 1.0 equiv) were reacted for 7 h to give a red-brown suspension




which, following the work-up described in the general procedure, gave a yellow oil (>99:1 dr).


loaded with 1.5 g SiO2, 99:1 petroleum ether/benzene (900 mL), ca. 10 mL fractions], followed

by further purification of the mixed fractions [46 g high porosity grade SiO2, 34 mm Ø, dry

loaded with 1.8 g SiO2, hexane (1.5 L), ca. 10 mL fractions], gave a colourless oil (287 mg).

Further purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 29q as a

clear, colorless oil (280 mg, 71%, contaminated with 4% vinylic chloride by-product). The 1H

and 13C NMR spectroscopic data matched that for alternative preparations.27

Data for 29q: bp: 171 °C (ABT) (0.05 mm Hg)


δ 7.70–7.64 (m, 4 H, HC(2′,2′′)), 7.48–7.38 (m, 6 H, HC(3′,3′′,4′4′′)), 4.47 (ddd, J =

9.0, 5.2, 2.1 Hz, 1 H, HC(3)), 4.07 (ddd, J = 7.8, 5.5, 2.2 Hz, 1 H, HC(2)), 3.98 (dd,

J = 10.3, 8.2 Hz, 1 H, HC(1)), 3.84 (dd, J = 10.3, 5.5 Hz, 1 H, HC(1)), 1.92 (ddt, J

= 14.3, 9.3, 4.7 Hz, 1 H, HC(4)), 1.86–1.77 (m, 1 H, HC(4)), 1.63–1.52 (m, 1 H,

HC(5)), 1.52–1.41 (m, 1 H, HC(5)), 1.07 (s, 9 H, Sit-Bu), 0.97 (t, J = 7.4 Hz, 3 H,

HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 135.6 & 135.5 (C(2′,2′′)), 133.0 & 132.8 (C(1′,1′′)), 129.9 (C(4′,4′′)), 127.82 &

127.80 (C(3′,3′′)), 64.9 (C(2)), 63.7 (C(1)), 61.2 (C(3)), 37.6 (C(4)), 26.8 (SiCMe3),

19.8 (SiCMe3), 19.2 (C(5)), 13.4 (C(6))

IR: (neat)

3072 (w), 3051 (w), 2999 (w), 2960 (m), 2933 (m), 2859 (m), 1590 (w), 1488 (w),

1472 (m), 1428 (m), 1391 (w), 1362 (w), 1274 (w), 1258 (w), 1189 (w), 1113 (s),

1008 (w), 999 (w), 937 (w), 920 (w), 881 (w), 824 (m), 760 (w), 740 (m), 702 (s),

650 (w), 613 (m)

MS: (ESI+ TOF)

431.1 ([M+Na]+, 10), 421.2 (15), 413.3 (48), 399.2 (17), 377.2 (11), 360.2 (20),

359.2 (100), 348.3 (10), 283.2 (37), 282.3 (28), 256.8 (16), 149.0 (14), 125.1 (10),

124.1 (91)




HRMS: (ESI+ TOF)


TLC: Rf 0.53 (MTBE/hexanes, 1%) [UV/KMnO4]

Preparation of tert-Butyl{[(u)-2,3-dichlorohexyl]oxy}diphenylsilane (29r) (Table 3)




alkene 28r (340 mg, 1.01 mmol, 1.0 equiv) were reacted for 9 h to give a yellow-brown


(99:1 dr). Purification via flash column chromatography [41 g high porosity grade SiO2, 30 mm

Ø, dry loaded with 1.5 g SiO2, 100:0 → 98:2 → 95:5 petroleum ether/Et2O (700 mL, 200 mL,

and 100 mL, respectively), ca. 10 mL fractions] gave a colourless oil (266 mg). Further

purification via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave 29r as a clear,

colorless oil (260 mg, 67%, >99:1 dr, contaminated with 1% vinylic chloride by-product). The 1H and 13C NMR spectroscopic data matched that for alternative preparations.27

Data for 29r: bp: 171 °C (ABT) (0.05 mm Hg)


δ 7.72–7.68 (m, 4 H, HC(2′,2′′)), 7.48–7.38 (m, 6 H, HC(3′,3′′,4′4′′)), 4.36 (ddd, J =

9.4, 6.3, 2.8 Hz, 1 H, HC(3)), 4.11–4.06 (m, 2 H, HC(1,2)), 3.91 (dd, J = 12.5, 6.5

Hz, 1 H, HC(1)), 1.94 (dddd, J = 12.8, 9.1, 6.2, 2.7 Hz, 1 H, HC(4)), 1.82–1.74 (m,

1 H, HC(4)), 1.72–1.83 (m, 1 H, HC(5)), 1.51–1.40 (m, 1 H, HC(5)), 1.08 (s, 9 H,

Sit-Bu), 0.96 (t, J = 7.4 Hz, 3 H, HC(6)) 13C NMR: (126 MHz, CDCl3)

δ 135.61 & 135.57 (C(2′,2′′)), 132.85 & 132.82 (C(1′,1′′)), 129.9 (C(4′,4′′)), 127.8




(C(3′,3′′)), 65.2 (C(2)), 65.1 (C(1)), 61.7 (C(3)), 35.9 (C(4)), 26.7 (SiCMe3), 19.3

(SiCMe3), 19.2 (C(5)), 13.5 (C(6))

IR: (neat)

2985 (w), 2952 (m), 2847 (w), 1726 (s), 1660 (m), 1436 (m), 1381 (w), 1327 (w),

1314 (w), 1273 (m), 1231 (w), 1202 (m), 1161 (m), 1105 (w), 1178 (w), 1040 (w),

989 (w), 914 (w), 856 (w), 922 (w), 792 (w), 721 (w), 698 (w), 650 (w), 614 (w)

MS: (ESI+ TOF)

414.3 (29), 413.3 (100), 409.3 ([M+H]+, 2), 392.3 (10), 391.3 (35). 339.3 (10),

338.3 (36), 279.2 (24), 167.0 (25), 149.0 (37), 113.1 (25)

HRMS: (ESI+ TOF)


TLC: Rf 0.56 (MTBE/hexanes, 1%) [UV/KMnO4]

Preparation of tert-Butyl{[(l)-2,3-dichloro-5-phenylpentyl]oxy}dimethylsilane (29s) and (l)-

2,3-Dichloro-5-phenylpentan-1-ol (29u) (Table 3)




alkene 28s (277 mg, 1.00 mmol, 1.0 equiv) were reacted for 6 h to give a yellow-brown


(>98:2 dr w.r.t. sum of 29s and the free alcohol dichloride 29u). Partial cleavage of the tert-

butyldimethylsilyl group was observed by 1H NMR spectroscopy of the crude mixture as a 2.3:1

mixture of 29s:29u. Purification via flash column chromatography [72 g SiO2, 34 mm Ø, dry

loaded with 2.5 g SiO2, 100:0 → 99.2:0.8 hexane/Et2O followed by 88:12 hexane/EtOAc (1 L, 1




L, and 1.1 L, respectively), ca. 10 mL fractions] gave 29s and 29u as pale yellow oils. Further

purification of the mixed fractions, containing 29s, via flash column chromatography [53 g high

porosity grade SiO2, 34 mm Ø, dry loaded with 2.2 g SiO2, 100:0 → 98:8:1.2 hexane/MTBE (2 L

and 500 mL, respectively), ca. 10 mL fractions then 25 g SiO2, 24 mm Ø, wet loaded, 100:0 →

95.5:0.5 → 99:1 hexane:Et2O (400 mL, 200 mL, and 200 mL, respectively), ca. 10 mL fractions]

gave a colourless oil (166 mg). Further purification via Kugelrohr distillation at reduced pressure

(0.05 mm Hg) gave 29s as a clear, colourless oil (163 mg, 47%). Further purification of 29u via

flash column chromatography [26 g SiO2, 24 mm Ø, wet loaded with CH2Cl2, 96:4 → 88:12

hexane/EtOAc (100 mL and 500 mL, respectively), ca. 10 mL fractions] gave 29u as a clear,

colourless oil (49.9 mg, 21%, contaminated with 3% vinylic chloride by-product). The 1H and 13C NMR spectroscopic data matched that for the catalytic syn-dichlorination of allylic alcohol

28u (vide infra).

Data for 29s: bp: 118 °C (ABT) (0.05 mm Hg)


δ 7.32–7.27 (m, 2 H, HC(2′)), 7.24–7.18 (m, 3 H, HC(3′,4′)), 4.29 (ddd, J = 9.9, 4.0,

2.0 Hz, 1 H, HC(3)), 4.01 (ddd, J = 7.5, 5.4, 2.0 Hz, 1 H, HC(2)), 3.87 (dd, J = 10.0,

8.6 Hz, 1 H, HC(1)), 3.78 (dd, J = 10.0, 5.4 Hz, 1 H, HC(1)), 2.90 (ddd, J = 13.6,

8.3, 5.2 Hz, 1 H, HC(5)), 2.77 (dt, J = 13.9, 8.1 Hz, 1 H, HC(5)), 2.34–2.24 (m, 1 H,

HC(4)), 2.09 (ddd, J = 18.2, 8.2, 4.0 Hz, 1 H, HC(4)), 0.84 (s, 9 H, Sit-Bu), 0.05 (s,

6 H, SiMe2) 13C NMR: (126 MHz, CDCl3)

δ 140.4 (C(1′)), 128.54 & 128.52 (C(2′,3′)), 126.2 (C(4′)), 64.3 (C(1)), 64.0 (C(2)),

60.4 (C(3)), 37.4 (C(4)), 32.5 (C(5)), 25.7 (SiCMe3), 18.1 (SiCMe3), –5.45 & –5.52

(SiMe2)

IR: (neat)

3087 (w), 3065 (w), 3028 (w), 2955 (m), 2929 (m), 2884 (w), 2857 (m), 1604 (w),

1497 (w), 1471 (m), 1463 (m), 1455 (m), 1433 (w), 1407 (w), 1390 (w), 1362 (w),

1258 (m), 1120 (s), 1006 (w), 996 (w), 939 (w), 838 (m), 815 (w), 779 (m), 749 (w),

699 (m), 667 (w), 624 (w), 615 (w)




MS: (ESI+, TOF)

437.2 (18), 416.2 (29), 415.2 (100), 399.3 (56), 390.2 (13), 362.2 (11), 356.2 (15),

349.2 (25), 347.2 ([M+H]+, 35), 282.3 (24), 275.2 (13), 179.1 (21), 156.1 (11),

143.1 (23), 119.1 (44)

HRMS: (ESI+, TOF)




Calcd: C, 58.78; H, 8.12%

Found: C, 59.07; H, 7.73%






sealed with a rubber septum, removed from the box, and placed under argon. MeCN (5.0 mL)

and chlorotrimethylsilane (Me3SiCl) (218 mg, 255 µL, 2.01 mmol, 2.0 equiv) were then added

sequentially and stirring was commenced. After ca. 10 min, an off-white suspension

(occasionally with yellow tinges) was observed. At this point, the requisite allylic alcohol (1.00

mmol, 1.0 equiv) was transferred via syringe to the reaction mixture [for allylic alcohols of

unknown density, only 3.0 mL of MeCN was added initially and the remaining 2.0 mL (in two

1.0 mL portions) was used to transfer the allylic alcohol across from an oven-dried, 4-mL dram

vial under an argon atmosphere, via syringe]. The resultant suspension was stirred at rt, and was

monitored by TLC until no allylic alcohol substrate could be detected. Once the reaction had

reached completion, sat. aq. NaHCO3 (1.0 mL) was added to quench any unreacted

chlorotrimethylsilane. After stirring for ca. 10 min at rt, the resultant mixture was transferred to a

separatory funnel and diluted with H2O (15 mL). The aqueous layer was extracted with Et2O (3 ×

15 mL), and the combined organic extracts were washed with brine (15 mL), then dried (MgSO4),

filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg). The resultant residue was re-




dissolved in EtOAc/Et2O (1:1 v/v, 5 mL) and eluted through a short plug of silica gel (ca. 0.55 g

SiO2 packed into a Pasteur pipet to a height of ca. 40 mm) to remove any ammonium salts, and

the plug was rinsed through with further portions of Et2O (3 × 5 mL) The solvent was removed

in vacuo (20–23 °C, ca. 20 mm Hg for non-volatile products or 5–8 °C, ca. 20 mm Hg for

volatile products), and an aliquot of the crude mixture was dissolved in CDCl3 to measure the

syn/anti diastereoisomeric ratio (dr) by 1H NMR spectroscopy. The syn-dichloride product was

then isolated as described.

Preparation of (l)-2,3-Dichlorohexan-1-ol (29t) (Table 3)

Following General Procedure VIII, PhSeSePh (15.8 mg, 0.05 mmol, 5 mol %), BnEt3NCl

(690 mg, 3.03 mmol, 3.0 equiv), 11 (241 mg, 1.30 mmol, 1.3 equiv), MeCN (5.0 mL), Me3SiCl

(218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and (E)-2-hexen-1-ol 28t (102 mg, 120 µL, 1.02 mmol,

1.0 equiv) were reacted for 14 h to give a clear, light yellow solution which, following the work-

up described in the general procedure, gave a yellow oil (99:1 dr). Purification via flash column

chromatography [26 g SiO2, 24 mm Ø, dry loaded with 1.2 g SiO2, 95:5 → 84:16 hexane/Et2O

(100 mL and 500 mL, respectively), ca. 10 mL fractions then 22 g SiO2, 24 mm Ø, wet loaded,


clear, slightly yellow oil (113 mg). Caution: the product is volatile at ca. 0.05 mm Hg. Further

purification via Kugelrohr distillation at reduced pressure (5 mm Hg) gave 29t as a clear,


Data for 29t: bp: 100 °C (ABT) (5 mm Hg)


δ 4.24 (ddd, J = 8.4, 6.0, 2.7 Hz, 1 H, HC(3)), 4.16 (td, J = 6.4, 2.7 Hz, 1 H, HC(2)),

3.95 (dt, J = 12.8, 6.6 Hz, 1 H, HC(1)), 3.92–3.85 (m, 1 H, HC(1)), 2.15–2.04 (m, 1

H, OH), 1.92–1.80 (m, 2 H, HC(4)), 1.65–1.53 (m, 1 H, HC(5)), 1.50–1.38 (m, 1 H,

HC(5)), 0.96 (t, J = 7.4 Hz, 3 H, HC(6))





δ 65.4 (C(2)), 64.5 (C(1)), 61.7 (C(3)), 37.2 (C(4)), 19.8 (C(5)), 13.4 (C(6))

IR: (neat)

3363 (m), 2962 (m), 2937 (m), 2876 (m), 1634 (w), 1465 (m), 1434 (w), 1383 (w),

1274 (w), 1135 (s), 1058 (m), 997 (w), 915 (w), 881 (w), 843 (w), 771 (w), 756 (w),

732 (w), 615 (m)

MS: (CI+, DFSF)

173.0 (12), 171.0 ([M+H]+, 18), 155.0 (18), 153.0 ([M–OH]+, 21), 119.0 (39), 117.0

([(M–HCl)–OH]+, 75), 106.0 (34), 104.0 (70), 99.1 (48), 91.0 (20), 89.0 (24), 81.1

({[(M–HCl)–OH]-HCl}+, 100), 75.0 (24), 69.1 (40), 68.1 (42), 57.1 (34), 55.1 (61)

HRMS: (CI+, DFSF)




Calcd: C, 42.13; H, 7.07%

Found: C, 42.13; H, 7.02%

Preparation of (l)-2,3-Dichloro-5-phenylpentan-1-ol (29u) (Table 3)



(218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and allylic alcohol 28u (162 mg, 1.00 mmol, 1.0 equiv)

were reacted for 9 h to give a clear, light yellow solution which, following the work-up described

in the general procedure, gave an orange oil (98:2 dr). Purification via flash column

chromatography [76 g SiO2, 34 mm Ø, dry loaded with 2.5 g SiO2, 95:5 → 85:15 hexane/EtOAc

(500 mL and 1 L, respectively), ca. 10 mL fractions then 72 g high porosity grade SiO2, 34 mm

Ø, wet loaded with CH2Cl2, 100:0 (not collected) → 91:9 hexane/acetone (100 mL and 800 mL,

respectively), ca. 10 mL fractions] gave 29u as a clear, colourless oil (173 mg, 76%). The




product 29u was obtained in three different fractions, each being contaminated with ≤6.5% of the

vinylic chloride by-product, (E)-3-chloro-5-phenylpent-2-en-1-ol: fraction I (T50–52, 51 mg,

93.5% purity), fraction II (T53–63, 83 mg, 97.5% purity), and fraction III (T64–82, 39 mg, 99%

purity).

Data for 29u (from fraction III): bp: 127 °C (ABT) (0.05 mm Hg)


δ 7.35–7.29 (m, 2 H, HC(2′)), 7.25–7.20 (m, 3 H, HC(3′,4′)), 4.21–4.13 (m, 2 H,

HC(2,3)), 3.97–3.84 (m, 2 H, HC(1)), 2.93 (ddd, J = 13.8, 8.6, 5.2 Hz, 1 H, HC(5)),

2.76 (dt, J = 13.9, 8.2 Hz, 1 H, HC(5)), 2.28–2.13 (m, 2 H, HC(4)), 2.05 (dd, J =

7.5, 5.3 Hz, 1 H, OH) 13C NMR: (126 MHz, CDCl3)

δ 140.2 (C(1′)), 128.6 & 128.5 (C(2′,3′)), 126.3 (C(4′)), 65.4 (C(2)), 64.4 (C(1)),

61.0 (C(3)), 36.8 (C(4)), 32.5 (C(5))

IR: (neat)

3554 (w), 3385 (m), 3086 (w), 3063 (w), 3027 (m), 2939 (m), 2863 (w), 1949 (w),

1875 (w), 1808 (w), 1603 (w), 1583 (w), 1496 (m), 1455 (m), 1432 (w), 1285 (w),

1267 (w), 1135 (m), 1101 (m), 1079 (m), 1031 (m), 996 (w), 910 (w), 840 (w), 782

(w), 751 (m), 700 (m), 623 (m)

MS: (EI+, TOF)

234.0 (17), 232.0 (M+, 27), 197.1 ([M–Cl]+, 10), 160.1 (10), 143.1 (64), 129.1 (26),

128.1 (19), 125.1 (16), 117.1 (22), 115.1 (16), 105.1 (23), 104.1 (48), 92.1 (18),

91.0 ([CH2Ph]+, 100), 65.0 (13)

HRMS: (EI+, TOF)

calcd for C11H14Cl2O (M+): 232.0422, found: 232.0427

TLC: 29u – Rf 0.38 (80:20 hexane/EtOAc) [UV/KMnO4]

vinylic chloride – Rf 0.32 (80:20 hexane/EtOAc) [UV/KMnO4]




Preparation of (u)-2,3-Dichloro-5-phenylpentan-1-ol (29v) (Table 3)



(218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and allylic alcohol 28v (163 mg, 1.00 mmol, 1.0 equiv)

were reacted for 9 h to give a clear, light yellow solution which, following the work-up described

in the general procedure, gave an orange oil (98:2 dr). Purification via flash column


(500 mL and 1.1 L, respectively), ca. 10 mL fractions then 74 g high porosity grade SiO2, 34 mm

Ø, wet loaded with CH2Cl2, 100:0 (not collected) → 96:4 (not collected) → 88:12 hexane/EtOAc

(100 mL, 100 mL, and 1 L, respectively), ca. 10 mL fractions] gave 29v as a clear, pale yellow

oil (166 mg, 71%). The product 29v was obtained in two different fractions, in which fraction II

was contaminated with the vinylic chloride by-product, (Z)-3-chloro-5-phenylpent-2-en-1-ol:

fraction I (T54–69, 136 mg), fraction II (T70–86, 30 mg, ca. 89% purity). Further purification of

29v from fraction I via Kugelrohr distillation at reduced pressure (0.05 mm Hg) gave a clear,

colorless oil (134 mg, 98.5% mass return).

Data for 29v (from fraction I): bp: 130 °C (ABT) (0.05 mm Hg)


δ 7.35–7.28 (m, 2 H, HC(2′)), 7.25–7.18 (m, 3 H, HC(3′,4′)), 4.13–4.06 (m, 2 H,

HC(2,3)), 4.01 (dd, J = 6.9, 3.7 Hz, 2 H, HC(1)), 2.96 (ddd, J = 13.9, 9.6, 4.6 Hz, 1

H, HC(5)), 2.77 (ddd, J = 13.7, 9.2, 7.4 Hz, 1 H, HC(5)), 2.47–2.38 (m, 1 H,

HC(4)), 2.14–2.04 (m, 1 H, HC(4)), 1.95 (t, J = 7.0 Hz, 1 H, OH) 13C NMR: (126 MHz, CDCl3)

δ 140.4 (C(1′)), 128.6 & 128.5 (C(2′,3′)), 126.3 (C(4′)), 66.3 (C(2)), 64.5 (C(1)),

60.8 (C(3)), 36.7 (C(4)), 31.8 (C(5))

IR: (neat)

3564 (w), 3390 (m), 3086 (w), 3063 (m), 3028 (w), 2931 (m), 2882 (w), 1948 (w),




1603 (w), 1497 (m), 1455 (m), 1433 (w), 1385 (w), 1240 (w), 1196 (w), 1105 (w),

1065 (m), 1030 (w), 966 (w), 908 (w), 839 (w), 775 (w), 750 (m), 700 (m), 655 (m)

MS: (EI+, TOF)

234.0 (19), 232.0 (M+, 33), 160.1 (11), 143.1 (66), 129.1 (28), 128.1 (21), 125.1

(20), 117.1 (28), 115.1 (18), 105.1 (21), 104.1 (57), 103.1 (11), 92.1 (29), 91.0

([CH2Ph]+, 100), 77.0 ([C6H5]+, 15), 65.0 (28)

HRMS: (EI+, TOF)

calcd for C11H14Cl2O (M+): 232.0422, found: 232.0425


Preparation of 4-(Benzyloxy)-(l)-2,3-dichlorobutan-1-ol (29w) and 4-(Benzyloxy)-(u)-2,3-

dichlorobutan-1-ol (29x) (Table 3)



(218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and allylic alcohol 28w (179 mg, 1.00 mmol, 1.0

equiv) were reacted for 47 h to give a light yellow solution with tinges of cloudiness. TLC

analysis showed that a trace amount of 28w remained. Following the work-up described in the

general procedure, an orange oil was obtained (56:44 29w:29x). (Note: 29w and its

diastereoisomeric dichloride 29x were inseparable on TLC despite numerous attempts with

different solvent systems). Purification via flash column chromatography [41 g high porosity

grade SiO2, 30 mm Ø, dry loaded with 1.5 g SiO2, 95:5 → 80:20 → 75:25 petroleum ether/Et2O

(120 mL, 1 L, and 200 mL, respectively), ca. 10 mL fractions then 28 g SiO2, 24 mm Ø, wet

loaded with CH2Cl2, 96:4 → 88:12 hexane/EtOAc (100 mL and 600 mL, respectively), ca. 10

mL fractions] gave a 56:44 mixture of 29w:29x as a clear, colourless, viscous oil (168 mg, 67%




combined, contaminated with 3% of an unidentified benzyloxy-containing impurity). The 1H and 13C NMR spectroscopic data of 29w matched that for alternative preparations.27,29

Data for mixture of 29w and 29x:


δ 7.40–7.29 (m, 5 H, HC(2′,3′,4′), 29w & 29x), 4.64 & 4.60 (ABq, JAB = 12.0 Hz, 2

H, HC(5′), 29x), 4.59 (s, 2 H, HC(5′), 29w), 4.45–4.37 (m, 2 H, HC(2′,3′), 29w),

4.36 (dt, J = 8.2, 4.3 Hz, 1 H, HC(2), 29x), 4.30 (dt, J = 8.0, 4.1 Hz, 1 H, HC(3),

29x), 4.07–3.96 (m, 2 H, HC(1), 29x), 3.95–3.84 (m, 2 H each for both 29w & 29x,

HC(1) for 29w, HC(4) for 29x), 3.83–3.75 (m, 2 H, HC(4), 29w), 2.26 (t, J = 7.0

Hz, 1 H, OH, 29x), 2.21 (dd, J = 7.7, 5.4 Hz, 1 H, OH, 29w) 13C NMR: (126 MHz, CDCl3)

δ 137.3 (C(1′), 29x), 137.2 (C(1′), 29w), 128.51 (C(3′), 29w), 128.47 (C(3′), 29x),

128.0 (C(4′), 29w), 127.9 (C(4′), 29x), 127.8 (C(2′), 29w), 127.7 (C(2′), 29x), 73.6,

(C(5′), 29w & 29x), 70.8 (C(4), 29x), 70.6 (C(4), 29w), 64.1 (C(1), 29w & 29x),

62.9 (C(2), 29x), 61.9 (C(2), 29w), 59.3 (C(3), 29x), 58.4 (C(3), 29w)

IR: (neat)

3404 (m), 3088 (w), 3064 (w), 3031 (w), 2936 (w), 2872 (m), 1604 (w), 1497 (w),

1455 (m), 1364 (m), 1310 (w), 1251 (w), 1207 (w), 1077 (m), 1029 (m), 911 (w),

861 (w), 790 (w), 740 (m), 698 (m), 665 (w), 607 (w)

MS: (ESI+, TOF)

342.0 (17), 341.0 (17), 303.0 (14), 251.1 (65), 250.1 (14), 249.1 ([M+H]+, 100),

158.0 (17), 130.0 (13), 91.1 ([CH2Ph]+, 91)

HRMS: (ESI+, TOF)






Preparation of 4-(Benzyloxy)-(u)-2,3-dichlorobutan-1-ol (29x) (Table 3)



(218 mg, 255 µL, 2.01 mmol, 2.0 equiv), and allylic alcohol 28x (179 mg, 1.00 mmol, 1.0 equiv)

were reacted for 15 h to give a clear, light yellow solution which, following the work-up

described in the general procedure, gave a yellow oil (93:7 dr). Purification via flash column


(100 mL and 400 mL, respectively), ca. 10 mL fractions], followed by further purification of the

mixed fractions [23 g SiO2, 24 mm Ø, dry loaded with 1.2 g SiO2, 96:4 → 88:12 hexane/EtOAc

(100 mL and 500 mL, respectively), ca. 10 mL fractions], gave 29x as a clear, colorless oil,

which solidified to a white solid on standing in a –20 °C freezer for ca. 1 day (181 mg, 73%,

96:4 dr). Further purification was performed via recrystallization from boiling Et2O (2 mL), with

gradual cooling to rt and, finally, to 0 °C in a 20 mL scintillation vial loosely sealed with a screw

top cap. The crystals were collected via filtration through filter paper in a Hirsch funnel under

house vacuum, washed with (–78 °C) hexane (3 × ca. 1 mL), crushed with a spatula, and dried in

vacuo (0.05 mm Hg) overnight to give a white, crystalline solid (138 mg). The filtrate was

concentrated in vacuo (20–23 °C, ca. 20 mm Hg) and the white solid recovered (52 mg) was re-

subjected to the same recrystallization conditions. The material from both crops was combined to

give 29x as a white, crystalline solid (170 mg, 94% mass return, 97:3 dr). The 1H and 13C NMR

spectroscopic data matched that for alternative preparations.27,29

Data for 29x: mp: 44–46 °C (Et2O) [lit: 36–40 °C (hexane/Et2O)]27



4.36 (dt, J = 8.2, 4.3 Hz, 1 H, HC(2)), 4.30 (dt, J = 8.0, 4.1 Hz, 1 H, HC(3)), 4.07–

3.96 (m, 2 H, HC(1)), 3.95–3.84 (m, 2 H, HC(4)), 2.21 (t, J = 7.0 Hz, 1 H, OH)





δ 137.3 (C(1′)), 128.47 (C(3′)), 127.9 (C(4′)), 127.7 (C(2′)), 73.6, (C(5′)), 70.8

(C(4)), 64.1 (C(1)), 62.9 (C(2)), 59.3 (C(3))

IR: (neat)

3361 (m), 3267 (m), 3065 (w), 3029 (w), 2937 (w), 2909 (w), 2872 (w), 1605 (w),

1495 (w), 1451 (w), 1404 (w), 1359 (m), 1308 (w), 1288 (w), 1238 (w), 1194 (w),

1140 (w), 1111 (w), 1086 (m), 1077 (w), 1044 (w), 1027 (w), 1003 (w), 931 (w),

731 (s), 694 (m), 655 (m)

MS: (ESI+, TOF)

271.0 ([M+Na]+, 10), 251.1 (52), 249.1 ([M+H]+, 76), 125.1 (15), 124.2 (24), 124.1

({[M–(OCH2Ph)]–OH}+, 100), 91.1 ([CH2Ph]+, 66)

HRMS: (ESI+, TOF)



Determination of Relative Configurations within Dichlorides (Table 3)

The relative configurations within the dichlorides prepared via catalytic syn-

dichlorination (Table 3) were determined as follows:

1. The relative configuration within dichloride 7 was assigned as syn by comparing the 1H

NMR spectroscopic data to that from a commercial sample of its diastereoisomeric

dichloride trans-1,2-dichlorocyclohexane (Aldrich, 99%) (all measurements in CDCl3).

2. The relative configurations within dichlorides 29q,r,w,x were assigned as syn by

comparing the 1H and 13C NMR spectroscopic data to those from known dichlorides (all

measurements in CDCl3).27,29

3. The relative configurations within dichlorides 29t-v were assigned as syn by comparing

the 1H chemical shifts for HC(1,2,3) within the dichlorides to those from the analogous

anti-dichloride (u)-2,3-dichloro-1-nonanol (all measurements in CDCl3).30

4. The relative configurations in syn-configured dichlorides 18, 14, 29j-n were assigned by

comparison of the vicinal dichloride 1H-1H 3J coupling constants of 3.0–3.3 Hz to that




measured for the known syn-dichloride (l)-2,3-dichlorooctane,28 which is also 3.0 Hz (all

measurements in CDCl3).

5. An authentic sample of the anti-configured dichloride 29i was prepared via an anti-

selective dichlorination of the (E)-alkene 13 with Cl2 (NMR experiment), and its1H NMR

data matched that for its preparation via a catalytic syn-dichlorination of the (Z)-alkene

28i. The measured vicinal dichloride 1H-1H 3J coupling constant of 6.5 Hz for 29i

contrasts with the value of ca. 3 Hz measured for its diastereoisomer 14. A similar

observation was made with the syn-configured dichloride 29j (3JHH = 3.2 Hz) and its

diastereoisomeric dichloride (3JHH = 6.3 Hz). Thus, the relative configurations within

anti-configured dichlorides 29h,p,o were all assigned based on measured vicinal chloride 1H-1H 3J coupling constants of 6.5–6.6 Hz (all measurements in CDCl3).

6. The relative configuration within dichloride 29s was assigned as syn by comparison of

the vicinal dichloride 1H-1H 3J coupling constant of 2.1 Hz to that measured for the

known syn-dichloride 29q, which has a 3JHH coupling constant of 2.2 Hz (all

measurements in CDCl3). An authentic sample of the diastereoisomeric dichloride of 29s

was prepared via an anti-selective dichlorination of the (E)-alkene 28s with Cl2 (NMR

experiment), and the vicinal chloride 1H-1H 3J coupling constant was measured as 6.5 Hz

– a similar value to that for anti-configured dichloride 29r (6.3 Hz).

7. The relative configuration within dichloride 29a [δ 4.41–4.39 (m, 2 H, HCCl(1,2))] was

assigned as syn by comparison to an authentic sample of the diastereoisomeric dichloride

[δ 4.29–4.25 (m, 2 H, HCCl(1,2))] prepared via an anti-selective dichlorination of

cycloheptene with Cl2 (NMR experiment).

8. The relative configuration within dichloride 29g [δ 4.07–4.04 (m, 2 H, HCCl(4,5))] was

assigned as syn by comparison to an authentic sample of the diastereoisomeric dichloride

[δ 4.02–3.97 (m, 2 H, HCCl(4,5))] prepared via an anti-selective dichlorination of (E)-4-

octene with Cl2 (NMR experiment).

9. The relative configurations within dichlorides 29b,c were assigned based on symmetry

considerations, as the syn-configured dichlorides would be meso-compounds. The four

sets of 1H and 13C signals within the [1r-(u)-3,4-dichlorocyclopentyl]methoxy moiety

confirmed the syn-assignment. The relative configuration at C(1) in 29c was, however,




assigned by comparison to an authentic sample of the syn-configured [at C(1)] dichloride,

prepared via a two-step oxidation-deoxochlorination sequence27 from tert-

butyl(cyclopent-3-en-1-ylmethoxy)diphenylsilane (28c), which matched identically. The

relative configuration at C(1) in 29b was in turn assigned via chemical correlation to 29c.

General Procedure IX: anti-Selective Dichlorination of Alkenes with Cl2

An oven-dried, 50-mL, three-necked, round-bottomed flask equipped with a magnetic

stirrer bar was charged with CDCl3 (pre-dried over 3Å molecular sieves, 5.0 mL) via syringe,

then was sealed with a glass stopper and weighed. One of the necks of the flask was connected to

a cylinder containing Cl2 gas, using Tygon® tubing and a Pasteur pipet, while another neck was

vented into a 250-mL Erlenmeyer flask containing 1 M aq. NaOH (50 mL) via Tygon® tubing.

Cl2 gas was gently bubbled into the CDCl3 over 1 min, with stirring, which gave a yellow

solution almost immediately (Note: gentle bubbling was important to minimize evaporation of

CDCl3). The Cl2 gas inlet was then disconnected, all three necks were sealed with a glass

stoppers, and the flask was re-weighed to measure the amount of Cl2 gas that had dissolved in the

CDCl3, thus allowing calculation of the concentration (ca. 0.78 M). (Note: the solution of Cl2 had

a limited lifetime; after ca. 2 h there was a significant loss in concentration, even in the dark). An

oven-dried NMR tube was then charged with the requisite alkene substrate (0.10 mmol, 1.0

equiv), CDCl3 (0.4 mL), and 1,1,2,2-tetrachloroethane (17.4 mg, 11 µL, 0.10 mmol, 1.0 equiv)

via syringe. The solution of Cl2 (130 µL, 0.10 mmol, 1.0 equiv) was then added dropwise via

syringe to the reaction mixture, with shaking at every drop. At the end of the addition, a pale

yellow solution was observed. The resultant mixture was shaken intermittently for 5 min and

then analysed by 1H NMR spectroscopy to obtain spectroscopic data on the corresponding anti-

configured vicinal dichloride. NMR yields were measured against 1,1,2,2-tetrachloroethane as an

internal standard.




Preparation of tert-Butyl{[(u)-4,5-dichlorohexyl]oxy}diphenylsilane (29i)

Following General Procedure IX, alkene 13 (33.9 mg, 0.10 mmol, 1.0 equiv), CDCl3 (0.4

mL), 1,1,2,2-tetrachloroethane (17.4 mg, 11 µL, 0.10 mmol, 1.0 equiv), and the freshly-prepared

CDCl3 solution of Cl2 (0.78 M, 130 µL, 0.10 mmol, 1.0 equiv) were reacted to give complete

conversion of 13 to anti-dichloride 29i (81% NMR yield). The 1H NMR spectroscopic data

matched that for the catalytic syn-dichlorination of (Z)-alkene 28i.

Preparation of tert-Butyl{[(u)-2,3-dichloro-5-phenylpentyl]oxy}dimethylsilane (S24) and

(u)-2,3-Dichloro-5-phenylpentan-1-ol (29v)

Following General Procedure IX, alkene 28s (27.6 mg, 0.10 mmol, 1.0 equiv), CDCl3

(0.4 mL), 1,1,2,2-tetrachloroethane (17.4 mg, 11 µL, 0.10 mmol, 1.0 equiv), and the freshly-

prepared CDCl3 solution of Cl2 (0.78 M, 130 µL, 0.10 mmol, 1.0 equiv) were reacted to give

complete conversion of 28s to anti-dichloride S24 (59% NMR yield). Partial cleavage of the tert-

butyldimethylsilyl group was also observed in the crude reaction mixture to give 29v (ca. 11%

NMR yield).

Data for S24: 1H NMR: (500 MHz, CDCl3, diagnostic resonances only)

δ 4.22 (ddd, J = 9.8, 6.5, 2.5 Hz, 1 H, HC(3)), 4.12–4.07 (m, 1 H, HC(2))




Preparation of {[(u)-4,5-Dichloro-7-phenylheptyl]oxy}tri-iso-propylsilane (S25)

Following General Procedure IX, alkene 28j (34.6 mg, 0.10 mmol, 1.0 equiv), CDCl3

(0.4 mL), 1,1,2,2-tetrachloroethane (17.4 mg, 11 µL, 0.10 mmol, 1.0 equiv), and the freshly-

prepared CDCl3 solution of Cl2 (0.80 M, 130 µL, 0.10 mmol, 1.0 equiv) were reacted to give

complete conversion of 28j to anti-dichloride S25 (60% NMR yield) and an unidentified by-

product (19% NMR yield).

Data for S25: 1H NMR: (500 MHz, CDCl3, diagnostic resonances only)


HC(5))

Preparation of (l)-1,2-Dichlorocycloheptane (S26)

Following General Procedure IX (with some modifications to the amounts of reagents),

cycloheptene 28a (19.4 mg, 23.5 µL, 0.20 mmol, 1.0 equiv), CDCl3 (0.4 mL), 1,1,2,2-

tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), and the freshly-prepared CDCl3

solution of Cl2 (0.63 M, 600 µL, 0.38 mmol, 1.9 equiv) were reacted to give complete conversion

of cycloheptene 28a to anti-dichloride S26 (91% NMR yield).

Data for S26: 1H NMR: (500 MHz, CDCl3)

δ 4.29–4.25 (m, 2 H, HC(1,2)), 2.24–2.17 (m, 2 H, HC(3,7)), 2.01–1.93 (m, 2 H,

HC(3,7)), 1.87–1.78 (m, 2 H, HC(4,6)), 1.64–1.53 (m, 4 H, HC(4,5,6))




Preparation of (u)-4,5-Dichlorooctane (S27)

Following General Procedure IX (with some modifications to the amounts of reagents),

(E)-4-octene 28g (22.5 mg, 31.5 µL, 0.20 mmol, 1.0 equiv), CDCl3 (0.4 mL), 1,1,2,2-

tetrachloroethane (33.3 mg, 21 µL, 0.20 mmol, 1.0 equiv), and the freshly-prepared CDCl3

solution of Cl2 (0.63 M, 600 µL, 0.38 mmol, 1.9 equiv) were reacted to give complete conversion

of (E)-4-octene 28g to anti-dichloride S27 (91% NMR yield).

Data for S27: 1H NMR: (500 MHz, CDCl3)

δ 4.02–3.97 (m, 2 H, HC(4,5)), 1.97–1.89 (m, 2 H, HC(3,6)), 1.82–1.73 (m, 2 H,

HC(3,6)), 1.69–1.60 (m, 2 H, HC(2,7)), 1.48–1.39 (m, 2 H, HC(2,7)), 0.95 (t, J =

7.4 Hz, 6 H, HC(1,8))

Preparation of tert-Butyl{[1r-(u)-3,4-dichlorocyclopentyl]methoxy}diphenylsilane (29c) via

a Two-Step Oxidation-Deoxochlorination Sequence

Preparation of (±)-{[(1R,3s,5S)-6-oxabicyclo[3.1.0]hexan-3-yl]methoxy}(tert-

butyl)diphenylsilane (S28). A flame-dried, 25-mL, round-bottomed flask equipped with a

magnetic stirrer bar was charged with tert-butyl(cyclopent-3-en-1-ylmethoxy)diphenylsilane 28c

(337 mg, 1.00 mmol, 1.0 equiv) then was sealed with a rubber septum and purged with argon via

an inlet needle. CH2Cl2 (5.0 mL) was added via syringe and the mixture was cooled in an ice-

water bath, with stirring, under an argon atmosphere. 3-Chloroperoxybenzoic acid (washed, 207

mg, 1.20 mmol, 1.2 equiv) was then added in one portion against a backflow of argon, and the

resultant mixture was allowed to stir in the ice-water bath for 30 min, followed by a further 1 h at




rt. The reaction mixture was then transferred to a separatory funnel, diluted with Et2O (20 mL),

and sequentially washed with sat. aq. Na2S2O3 (5 mL), sat. aq. NaHCO3 (10 mL), H2O (10 mL)

and brine (10 mL), then dried (MgSO4), filtered, and concentrated in vacuo (20–23 °C, ca. 20

mm Hg) to give a colourless oil [3.7:1 dr at C(3)]. Purification via flash column chromatography

[24 g SiO2, 24 mm Ø, dry loaded with 1.8 g SiO2, 100:0 → 96:4 hexane/EtOAc (100 mL and

300 mL, respectively), ca. 10 mL fractions] gave S28 as a white solid [313 mg, 89%, 3.7:1 dr at

C(3)].

Data for S28 mp: 68–72 °C

1H NMR: (500 MHz, CD3C1)

δ 7.67–7.62 (m, 4 H, HC(2′,2′′), both diastereoisomers), 7.45–7.35 (m, 6 H,

HC(3′,3′′,4′,4′′), both diastereoisomers), 3.60 (d, J = 5.3 Hz, 2 H, HC(6), major

diastereoisomer), 3.50 (d, J = 8.2 Hz, 2 H, minor diastereoisomer), 3.48 (s, 2 H,

HC(1,5), major diastereoisomer), 3.45 (s, 2 H, HC(1,5), minor diastereoisomer),

2.37–2.28 (m, 1 H, HC(3), minor diastereoisomer), 2.11 (dd, J = 13.5, 7.5 Hz, 2 H,

HC(2,4), major diastereoisomer), 2.14–1.99 (m, 1 H, HC(3), major

diastereoisomer), 1.91 (dd, J = 14.9, 1.5 Hz, 2 H, HC(2,4), minor diastereoisomer),

1.80 (dd, J = 14.9, 9.3 Hz, 2 H, HC(2,4), minor diastereoisomer), 1.53 (dd, J = 13.5,

9.1 Hz, 2 H, HC(2,4), major diastereoisomer), 1.05 (s, 9H, Sit-Bu, both

diastereoisomers). 13C NMR: (126 MHz, CD3C1)

δ 135.5 (C(2′,2′′), both diastereoisomers), 134.1 (C(1′,1′′), minor diastereoisomer),

133.7 (C(1′,1′′), minor diastereoisomer), 129.6 (C(4′,4′′), major diastereoisomer),

129.5 (C(4′,4′′), minor diastereoisomer), 127.6 (C(3′,3′′), major diastereoisomer),

127.5 (C(3′,3′′), minor diastereoisomer), 69.5 (C(6), minor diastereoisomer), 65.7

(C(6), major diastereoisomer), 58.6 (C(1,5), minor diastereoisomer), 57.1 (C(1,5),

major diastereoisomer), 38.1 (C(3), minor diastereoisomer), 35.3 (C(3), major

diastereoisomer), 30.7 (C(2,4), major diastereoisomer), 29.8 (C(2,4), minor

diastereoisomer), 26.9 (SiCMe3, minor diastereoisomer), 26.8 (SiCMe3, major

diastereoisomer), 19.3 (SiCMe3, both diastereoisomers)




IR: (neat)

3069 (w), 3028 (w), 2951 (m), 2929 (m), 2856 (m), 1588 (w), 1471 (m), 1429 (m),

1376 (m), 1361 (w), 1271 (w), 1201 (w), 1112 (s), 1016 (m), 998 (w), 945 (w),

915 (w), 840 (w), 827 (m), 791 (m), 744 (m), 703 (s), 688 (m), 615 (m)

MS: (ESI+, TOF)

354.2 (18), 353.2 ([M+H]+, 59), 275.2 ([M–Ph]+, 21), 269.2 (10), 233.1 (10), 97.1

([C5H7CH2O]+, 100)

HRMS: (ESI+, TOF)

calcd for C22H29O2Si ([M+H]+): 353.1937, found: 353.1939

TLC: minor diastereoisomer – Rf 0.31 (99:1 hexane/MTBE) [UV/KMnO4]

major diastereoisomer – Rf 0.33 (99:1 hexane/MTBE) [UV/KMnO4]

Preparation of tert-Butyl{[1r-(u)-3,4-dichlorocyclopentyl]methoxy}diphenylsilane

(29c). Following the procedure reported by Yoshimitsu et al.,27 a flame-dried, 25-mL, two-

necked, round-bottomed flask equipped with a magnetic stirrer bar, a glass stopper, and a reflux

condenser (attached at the top to an argon inlet) was charged with S28 (285 mg, 0.81 mmol, 1.0

equiv) and toluene (8.5 mL) via syringe. Triphenylphosphine (637 mg, 2.43 mmol, 3.0 equiv)

and N-chlorosuccinimide (324 mg, 2.43 mmol, 3.0 equiv) were then added sequentially against a

backflow of argon, and the resultant suspension was heated at 90 °C, with stirring (the reaction

quickly darkened to a black-purple mixture). The reaction mixture was allowed to cool to rt and

was quenched with sat. aq. NaHCO3 (1 mL), diluted with H2O (10 mL) and transferred to a

separatory funnel. The mixture was extracted with EtOAc (3 × 10 mL) and the combined organic

extracts were washed with brine (10 mL), then dried (MgSO4), filtered, and concentrated in

vacuo (20–23 °C, ca. 20 mm Hg) to give a yellow gum. Attempted purification via flash column

chromatography failed to separate the dichloride from the remaining triphenylphosphine, and the

resultant mixture (725 mg) was re-dissolved in EtOAc (5 mL). Sat.aq. NaHCO3 (1 mL) and tert-

butyl hydroperoxide (30 wt% in H2O, 0.5 mL) were then added via syringe. The biphasic

mixture was vigorously stirred for ca. 10 min at rt, then was quenched with sat. aq. Na2SO3 (0.5

mL), diluted with H2O (10 mL), transferred to a separatory funnel, and extracted with Et2O (3 ×

10 mL). The combined organic extracts were washed with brine (10 mL), then dried (MgSO4),

filtered, and concentrated in vacuo (20–23 °C, ca. 20 mm Hg) to give a pale yellow oil [3.6:1 dr




at C(1)]. Purification via flash column chromatography [27 g high porosity grade SiO2, 24 mm

Ø, dry loaded with 1.8 g silica, 100:0 → 99:1 hexane/MTBE (200 mL and 500 mL,

respectively), ca. 10 mL fractions] gave 29c as a colourless, viscous oil [289 mg, 71%, 3.1:1 dr

at C(1)]. The 1H and 13C NMR spectroscopic data for the major syn-diastereoisomer [at C(1)]

matched that for 29c obtained via direct, catalytic syn-dichlorination of tert-butyl(cyclopent-3-

en-1-ylmethoxy)diphenylsilane (28c) (vide supra). The respective 1H chemical shifts and vicinal 1H-1H 3J coupling constants of HC(6) between the syn- and anti- diastereoisomers [at C(1)] of

29c were used to assign a syn-configuration within the related compound [1r-(u)-3,4-

dichlorocyclopentyl]methyl acetate 29b (vide supra).26

Determination of Configurations within Vinylic Chlorides (Figure 2)

Preparation of (E)-tert-Butyl[(4-chlorohex-4-en-1-yl)oxy]diphenylsilane (15) and (E)-tert

Butyl[(5-chlorohex-4-en-1-yl)oxy]diphenylsilane (16) (Figure 2)










sequentially and stirring was commenced. After ca. 5 min, alkene 13 (339 mg, 1.00 mmol, 1.0

equiv) was added via cannula transfer under argon using two 1.0 mL portions of MeCN, and the

resultant mixture was stirred at rt for 18 h. Sat. aq. NaHCO3 (0.5 mL) was added to quench any

unreacted Me3SiCl, and 30% aq. H2O2 (10 µL, ca. 0.1 mmol) was added subsequently to

decompose any traces of β-chloro phenylselanyl products to the corresponding alkenes. After

stirring for ca. 10 min at rt, sat. aq. Na2SO3 (0.5 mL), H2O (10 mL) and CH2Cl2 (10 mL) were

sequentially added, and the layers were separated. The aqueous layer was extracted with CH2Cl2

(2 × 10 mL) and the combined organic extracts were dried (MgSO4), filtered, and concentrated in

vacuo (45 °C, ca. 5 mm Hg). The resultant residue was eluted through SiO2 to remove any

ammonium salts (10 g SiO2, 20 mm Ø, CH2Cl2, ca. 5 mL fractions) to give a 78:12:10 mixture of

14:15:16 as a yellow oil (408 mg). Purification via flash column chromatography (40 g high

porosity grade SiO2, 30 mm Ø, 99:1 hexane/MTBE, ca. 5 mL fractions), followed by further

purification of the mixed fractions (2 × 20 g high porosity grade SiO2, 20 mm Ø, 99:1

hexane/MTBE, ca. 2.5 mL fractions), gave, in order of elution, a 59:41 mixture of 15:16 as a

pale yellow oil (52.6 mg, 14%) and 14 as a colorless oil (260 mg). Further purification of 14 via

Kugelrohr distillation at reduced pressure [160 °C (ABT), 10–5 mm Hg] gave 14 as a clear,

colorless oil (257 mg, 63%, >99:1 dr, contaminated with 4% of an unidentified terminal alkene

impurity). The mixture of 15 and 16 was dissolved in CDCl3 and subjected to 1D NOESY

experiments, which established their configurations as (E) (see reciprocal enhancements

highlighted in blue, above).

Data for mixture of 15 and 16: 1H NMR: (500 MHz, CDCl3)

δ 7.69–7.64 (m, 4 H each, HC(2ʹ,2ʹʹ), 15 & 16), 7.46–7.36 (m, 6 H each,

HC(3ʹ,3ʹʹ,4ʹ,4ʹʹ), 15 & 16), 5.65 (q, J = 7.1 Hz, 1 H, HC(5), 15), 5.56 (t, J = 7.9 Hz,

1 H, HC(4), 16), 3.71–3.64 (m, 2 H each, HC(1), 15 & 16), 2.49 (t, J = 7.4 Hz, 2 H,

HC(3), 15), 2.15 (app q, J = 7.5 Hz, 2 H, HC(3), 16), 2.04 (s, 3 H, HC(16)), 1.82–

1.76 (m, 2 H, HC(2), 15), 1.65 (d, J = 7.1 Hz, 3 H, HC(6), 15), 1.64–1.58 (m, 2 H,

HC(2), 16), 1.06 (s, 9 H each, Sit-Bu, 15 & 16) 13C NMR: (125 MHz, CDCl3)

δ 135.5 (C(2ʹ,2ʹʹ), 15 & 16), 133.9, 133.8, 133.8 (C(1ʹ,1ʹʹ) for 15 & 16, C(4) for 15,

C(5) for 16), 129.5, 129.5 (C(4ʹ,4ʹʹ), 15 & 16), 127.6, 127.6 (C(3ʹ,3ʹʹ), 15 & 16),




127.3 (C(4), 16), 122.5 (C(5), 15), 62.8, 62.5 (C(1), 15 & 16), 32.0 (C(2), 16), 30.1

(C(2), 15), 29.7 (C(3), 15), 26.8 (SiCMe3, 15 & 16), 25.0 (C(3), 16), 20.7 (C(6), 16),

19.2 (SiCMe3, 15 & 16), 13.8 (C(6), 15)

MS: (EI+, DFSF)

373.2 ([M+H]+, 4), 337.2 (20), 317.1 (29), 316.1 (19), 315.1 (78), 297.1 (17), 296.1

(10), 295.1 (46), 287.1 (11), 281.1 (15), 269.1 (38), 267.1 (16), 261.1 (12), 254.1

(16), 253.1 (72), 240.1 (12), 239.1 (53), 233.1 (44), 217.0 (24), 199.0 (13), 197.0

(13), 191.1 (21), 181.1 (14), 179.1 (11), 157.1 (11), 135.0 (10), 117.0 (27), 99.1

(23), 92.1 (21), 91.1 (100), 81.1 (52), 75.0 (12)

HRMS: (ESI+, TOF)

calcd for C22H30ClOSi ([M+H]+): 373.1754, found: 373.1768

Preparation of (Z)-tert-Butyl[(4-chlorohex-4-en-1-yl)oxy]diphenylsilane (S29) and (Z)-tert-

Butyl[(5-chlorohex-4-en-1-yl)oxy]diphenylsilane (S30)










sequentially and stirring was commenced. After ca. 5 min, alkene 28i (339 mg, 1.00 mmol, 1.0

equiv) was added via cannula transfer under argon using two 1.0 mL portions of MeCN, and the

resultant mixture was stirred at rt for 18 h. Sat. aq. NaHCO3 (0.5 mL) was added to quench any

unreacted Me3SiCl, and 30% aq. H2O2 (10 µL, ca. 0.1 mmol) was added subsequently to

decompose any traces of β-chloro phenylselanyl products to the corresponding alkenes. After

stirring for ca. 10 min at rt, sat. aq. Na2SO3 (0.5 mL), H2O (10 mL) and CH2Cl2 (10 mL) were

sequentially added, and the layers were separated. The aqueous layer was extracted with CH2Cl2

(2 × 10 mL) and the combined organic extracts were dried (MgSO4), filtered, and concentrated in

vacuo (45 °C, ca. 5 mm Hg). The resultant residue was eluted through SiO2 to remove any

ammonium salts (10 g SiO2, 20 mm Ø, CH2Cl2, ca. 5 mL fractions) to give a 77:12:11 mixture of

29i:S29:S30 as a yellow oil (397 mg). Purification via flash column chromatography (40 g high

porosity grade SiO2, 30 mm Ø, 99:1 hexane/MTBE, ca. 5 mL fractions), followed by further

purification of the mixed fractions (40 g high porosity grade SiO2, 30 mm Ø, 99:1 hexane/MTBE,

ca. 5 mL fractions), gave, in order of elution, a 57:43 mixture of S29:S30 as a pale yellow oil

(61.2 mg, 16%) and 29i as a colorless oil (263 mg). Further purification of 29i via Kugelrohr

distillation at reduced pressure [160 °C (ABT), 10–5 mm Hg] gave 29i as a clear, colorless oil

(258 mg, 63%, >99:1 dr). The mixture of S29 and S32 was dissolved in CDCl3 and subjected to

1D NOESY experiments, which established their configurations as (Z) (see reciprocal

enhancements highlighted in blue, above).

Data for mixture of S29 and S30: 1H NMR: (500 MHz, CDCl3)

δ 7.69–7.65 (m, 4 H each, HC(2ʹ,2′′), S29 & S30), 7.45–7.36 (m, 6 H each,

HC(3ʹ,3′′,4′,4′′), S29 & S30), 5.50 (q, J = 6.6 Hz, 1 H, HC(5), S29), 5.41 (tq, J = 7.0,

1.3 Hz, 1 H, HC(4), S30), 3.69–3.65 (m, 2 H each, HC(1), S29 & S30), 2.44 (t, J =

7.3 Hz, 2 H, HC(3), S29), 2.28–2.22 (m, 2 H, HC(3), S30), 2.06 (app q, J = 1.3 Hz,

3 H, HC(6), S30), 1.83–1.77 (m, 2 H, HC(2), S29), 1.69 (dt, J = 6.5, 1.2 Hz, 3 H,

HC(6), S29), 1.67–1.61 (m, 2 H, HC(2), S30), 1.06 (s, 9 H each, Sit-Bu, S29 &

S30) 13C NMR: (125 MHz, CDCl3)

δ 135.7, 135.7 (C(2ʹ,2′′), S29 & S30), 135.3, 134.2, 134.1 (C(1ʹ,1′′) for S29 & S30,

C(4) for S29, C(5) for S30), 129.7, 129.7 (C(4ʹ,4′′), S29 & S30), 127.8, 127.7




(C(3ʹ,3′′), S29 & S30), 125.6 (C(4), S30), 120.2 (C(5), S29), 63.5, 62.7 (C(1), S29

& S30), 36.0 (C(3), S29), 31.7 (C(2), S30), 30.5 (C(2), S29), 27.0 (SiCMe3, S29 &

S30), 26.3 (C(6), S30), 25.4 (C(3), S30), 19.4, 19.4 (SiCMe3, S29 & S30), 14.1

(C(6), S29)

MS: (CI+, DFSF)

373.1 ([M+H]+, 7), 337.2 (29), 317.1 (36), 316.1 (23), 315.1 (100), 297.1 (21),

296.1 (13), 295.1 (59), 287.0 (22), 281.1 (15), 269.1 (23), 267.1 (25), 261.1 (12),

240.1 (11), 239.1 (50), 219.0 (12), 217.0 (34), 199.0 (11), 197.0 (15), 157.1 (15),

117.0 (30), 99.1 (13), 81.1 (79)

HRMS: (ESI+, TOF)

calcd for C22H30C2OSi ([M+H]+): 373.1754, found: 373.1757




Table of Problematic Substrates







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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.97

2.10

2.07

1.06

2.00

2.00

2.04

2.07

2.08

2.10

2.11

2.44

2.44

2.45

2.46

2.47

2.48

2.48

2.50

2.50

2.50

2.55

2.56

2.57

2.58

2.58

2.59

2.60

2.61

2.63

2.63

2.64

3.96

3.98

5.64

7.26

Cresswell, Eey and Denmark S128NATURE CHEMISTRY | www.nature.com/naturechemistry 128© 2015 Macmillan Publishers Limited. All rights reserved

0102030405060708090100110120130140150160170180190200f1 (ppm)

20.9

35.7

35.9

68.1

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

129.

3

171.

2


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.28

2.00

2.00

0.99

2.00

1.83

5.97

3.96

1.07

2.14

2.15

2.18

2.42

2.44

2.45

2.47

2.52

2.53

2.55

2.56

2.58

2.59

3.58

3.59

3.60

3.60

5.66

5.66

7.26

7.38

7.39

7.41

7.42

7.44

7.45

7.68

7.68

7.69

7.69

7.70

7.70


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.3

26.9

35.5

39.4

67.7

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

612

9.5

129.

613

4.1

135.

6


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

8.94

2.00

2.00

2.00

0.99

6.17

4.05

1.09

2.33

2.34

2.34

2.35

2.35

2.35

2.36

2.36

2.37

2.37

2.38

2.38

3.74

3.75

3.76

5.04

5.04

5.06

5.06

5.06

5.07

5.08

5.10

5.11

5.11

5.11

5.83

5.84

5.85

5.86

5.86

5.88

5.89

5.89

5.90

5.91

7.26

7.39

7.40

7.40

7.41

7.41

7.43

7.43

7.44

7.44

7.45

7.45

7.46

7.46

7.47

7.47

7.70

7.71

7.71

7.72

7.72

7.72

7.73


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.2

26.8

37.2

63.5

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

116.

3

127.

612

9.5

133.

913

5.4

135.

6


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.95

1.99

1.94

1.95

1.97

0.97

0.99

1.00

4.03

1.61

1.62

1.63

1.63

1.67

1.68

1.70

1.71

1.72

2.13

2.13

2.13

2.15

2.16

2.16

2.16

2.17

2.18

2.18

3.48

3.49

3.51

4.52

5.36

5.37

5.37

5.38

5.39

5.39

5.39

5.40

5.40

5.41

5.41

5.42

5.42

5.42

5.45

5.45

5.45

5.46

5.46

5.47

5.47

5.48

5.48

5.49

5.50

5.50

5.51

5.51

7.27

7.28

7.28

7.29

7.30

7.31

7.31

7.32

7.33

7.34

7.35

7.36


0102030405060708090100110120130140150160170180190200f1 (ppm)

12.7

23.4

29.5

69.8

72.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

124.

312

7.4

127.

612

8.3

129.

9

138.

6


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.01

5.00

1.99

2.00

2.00

6.08

4.03

1.06

1.60

1.62

1.63

1.64

1.66

2.07

2.08

2.09

2.11

3.66

3.67

3.69

5.37

5.38

5.40

5.41

5.41

5.42

5.42

5.43

5.45

5.46

7.26

7.37

7.38

7.39

7.40

7.42

7.42

7.43

7.44

7.45

7.45

7.68

7.68

7.69

7.70


0102030405060708090100110120130140150160170180190200f1 (ppm)

17.9

19.2

26.8

28.8

32.4

63.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

125.

012

7.6

129.

513

0.9

134.

113

5.6


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.03

5.00

1.98

2.02

2.00

6.13

4.08

1.09

1.62

1.63

1.64

1.64

1.64

1.65

1.66

1.68

2.15

2.16

2.18

2.19

3.69

3.71

3.72

5.37

5.37

5.38

5.38

5.39

5.39

5.40

5.40

5.41

5.42

5.44

5.46

5.48

5.48

5.49

5.49

5.50

5.51

7.26

7.39

7.39

7.40

7.41

7.42

7.43

7.44

7.44

7.45

7.45

7.46

7.46

7.46

7.70

7.70

7.71

7.72

7.72


0102030405060708090100110120130140150160170180190200f1 (ppm)

12.7

19.2

23.2

26.9

32.5

63.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

124.

112

7.6

129.

513

0.1

134.

113

5.6


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

22.5

0

2.01

1.99

1.97

2.00

2.00

1.98

3.02

2.39

1.04

1.05

1.06

1.07

1.07

1.08

1.09

1.10

1.11

1.56

1.58

1.59

1.61

1.62

2.04

2.06

2.07

2.08

2.28

2.30

2.31

2.31

2.33

2.65

2.67

2.68

3.65

3.67

3.68

5.42

5.44

5.46

5.46

5.47

5.47

5.47

5.48

5.50

5.51

7.17

7.18

7.18

7.19

7.26

7.26

7.28

7.29


0102030405060708090100110120130140150160170180190200f1 (ppm)

12.0

18.0

28.8

32.8

34.5

36.1

62.8

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

125.

712

8.2

128.

412

9.6

130.

6

142.

2


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.00

1.98

1.17

5.09

2.00

2.00

1.97

0.82

0.83

0.83

0.84

0.85

0.85

0.96

0.97

0.98

0.98

0.98

0.99

1.56

1.57

1.58

1.59

1.60

1.61

1.61

1.63

1.65

1.66

1.68

1.69

1.71

2.02

2.04

2.05

2.07

4.04

4.06

4.07

5.37

5.38

5.40

5.41

5.42

5.43

5.44

5.45

5.46

5.47

5.49

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

8.3

12.9

17.9

28.5

28.8

64.0

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

125.

7

130.

0

174.

9


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.06

2.00

2.03

1.99

2.00

2.04

1.15

2.03

1.60

1.60

1.61

1.61

2.21

2.22

2.23

2.24

2.25

2.25

2.49

2.50

2.52

3.68

5.32

5.32

5.33

5.33

5.35

5.35

5.36

5.36

5.37

5.38

5.39

5.39

5.40

5.41

5.42

5.43

5.44

5.45

5.45

7.19

7.19

7.21

7.21

7.25

7.25

7.26

7.26

7.28

7.28

7.28

7.32

7.33

7.34

7.35


0102030405060708090100110120130140150160170180190200210f1 (ppm)

17.8

26.7

41.7

50.2

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

125.

912

6.9

128.

712

9.4

129.

413

4.2

207.

8


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.04

2.04

1.97

1.98

2.00

2.00

1.97

0.96

4.32

1.62

1.62

1.63

1.63

1.65

1.66

1.67

1.67

1.68

2.08

2.09

2.10

2.10

2.11

2.11

2.12

2.12

2.89

3.66

3.68

3.69

3.69

3.70

3.70

3.71

3.73

3.84

3.86

3.86

3.87

3.87

3.87

3.88

3.90

5.36

5.37

5.39

5.40

5.41

5.41

5.42

5.43

5.44

5.45

5.46

7.20

7.21

7.21

7.22

7.22

7.22

7.23

7.23

7.24

7.25

7.26

7.26

7.27

7.27

7.28

7.28

7.29

7.29

7.29


0102030405060708090100110120130140150160170180190200210f1 (ppm)

17.9

26.6

37.8

43.9

65.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

111.

1

124.

812

6.3

127.

913

0.5

130.

8

136.

8


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.07

2.00

2.08

3.00

2.04

0.99

1.01

1.63

1.63

1.64

1.64

1.64

1.65

2.11

2.12

2.14

2.15

2.23

2.24

2.26

2.27

3.72

5.36

5.36

5.37

5.38

5.38

5.39

5.39

5.40

5.41

5.41

5.42

5.42

5.43

5.44

5.45

5.46

5.47

5.48

5.49

5.50

5.50

5.80

5.80

5.81

5.83

5.84

5.84

6.93

6.94

6.95

6.96

6.97

6.99

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

17.9

30.9

32.2

51.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

121.

0

126.

112

9.5

149.

0

167.

1


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.06

5.07

1.98

2.05

2.00

1.92

2.66

1.81

1.45

1.52

1.54

1.55

1.57

1.58

1.93

1.94

1.94

1.95

1.95

1.98

1.99

2.01

2.02

3.18

3.19

3.20

4.42

5.34

5.34

5.36

5.36

5.37

5.37

5.38

5.38

5.39

5.39

5.42

5.42

5.43

5.44

5.45

5.45

5.47

5.48

5.48

5.48

7.25

7.26

7.27

7.32

7.34

7.35


0102030405060708090100110120130140150160170180190200f1 (ppm)

0.8

CD3C

N1.

0 CD

3CN

1.2

CD3C

N1.

3 CD

3CN

1.5

CD3C

N1.

7 CD

3CN

1.8

CD3C

N

13.1

25.1

29.0

29.1

47.7

51.4

80.1

118.

0

125.

212

8.1

128.

512

9.5

131.

0

140.

4

156.

7


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.96

2.02

1.92

1.99

0.99

1.01

2.00

1.99

1.55

1.56

1.57

1.57

1.69

1.70

1.72

1.73

1.75

2.06

2.07

2.09

2.10

3.65

3.66

3.67

5.32

5.33

5.33

5.33

5.34

5.34

5.35

5.35

5.35

5.36

5.36

5.37

5.38

5.38

5.40

5.41

5.41

5.42

5.42

5.42

5.43

5.43

5.43

5.44

5.44

5.45

5.45

5.46

5.46

5.47

5.47

7.26

7.66

7.66

7.67

7.68

7.68

7.69

7.69

7.70

7.79

7.79

7.80

7.80

7.81

7.81

7.82

7.82


-100102030405060708090100110120130140150160170180190200210220f1 (ppm)

12.7

24.2

28.2

37.6

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

123.

012

4.8

129.

013

2.1

133.

7

168.

3


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.94

9.07

1.98

2.00

1.94

1.00

0.98

6.09

4.01

0.90

0.92

0.93

1.08

1.37

1.38

1.40

1.41

1.43

1.44

2.00

2.00

2.01

2.03

2.04

2.04

4.17

4.18

4.18

4.18

4.19

5.54

5.54

5.54

5.56

5.57

5.57

5.58

5.58

5.58

5.59

5.59

5.64

5.64

5.65

5.65

5.66

5.66

5.67

5.67

5.68

5.68

5.69

5.70

5.70

7.26

7.37

7.38

7.38

7.39

7.39

7.40

7.42

7.42

7.42

7.43

7.43

7.44

7.45

7.45

7.70

7.70

7.71

7.72

7.72


0102030405060708090100110120130140150160170180190200f1 (ppm)

13.7

19.2

22.4

26.9

34.3

64.7

76.7

77.0

77.3

127.

512

7.6

128.

812

9.5

131.

213

3.9

135.

6


-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

6.00

9.04

1.97

2.00

1.98

0.99

1.00

3.01

2.04

0.08

0.08

0.08

0.08

0.09

0.09

0.92

0.92

0.93

0.93

0.93

0.93

2.35

2.36

2.36

2.37

2.37

2.37

2.37

2.38

2.38

2.38

2.39

2.40

2.40

2.40

2.70

2.71

2.72

2.73

4.13

4.13

4.14

4.14

4.14

4.14

4.15

4.15

5.58

5.58

5.60

5.61

5.61

5.62

5.62

5.69

5.70

5.71

5.73

5.73

7.18

7.18

7.19

7.19

7.19

7.20

7.20

7.21

7.21

7.21

7.26

7.28

7.29

7.29

7.29

7.30

7.30

7.31

7.31


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.1

18.4

26.0

34.0

35.6

63.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

125.

712

8.2

128.

412

9.8

130.

2

141.

9


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.05

2.04

1.97

2.00

1.91

4.96

1.74

4.03

4.04

4.04

4.05

4.05

4.14

4.15

4.15

4.16

4.53

4.65

5.82

5.83

5.84

5.85

5.86

5.87

5.89

5.90

5.91

5.92

5.93

5.94

7.27

7.28

7.28

7.29

7.30

7.31

7.31

7.34

7.35


0102030405060708090100110120130140150160170180190200f1 (ppm)

62.9

70.0

72.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

612

7.712

8.4

132.

2

138.

1


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.00

4.03

4.06

3.81

6.80

6.82

7.26

7.50

7.51


0102030405060708090100110120130140150160170180190200f1 (ppm)

55.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

114.

7

122.

0

135.

413

5.4

135.

4

160.

1


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.00

2.00

2.07

1.99

2.00

3.91

6.81

6.81

6.83

6.83

6.86

6.86

6.87

6.88

6.89

6.89

7.20

7.20

7.21

7.21

7.21

7.21

7.23

7.23

7.26

7.55

7.55

7.56

7.57


0102030405060708090100110120130140150160170180190200f1 (ppm)

55.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

110.

1

118.

612

1.9

128.

113

0.6

156.

8


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.06

4.05

2.00

2.00

1.39

1.40

1.41

1.42

1.43

1.43

1.44

1.45

1.45

1.46

1.76

1.77

1.78

1.78

1.79

1.81

1.81

1.82

1.83

1.84

1.86

1.87

1.88

2.09

2.09

2.10

2.10

2.11

2.13

2.13

2.14

2.15

4.27

4.28

4.28

4.29

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

22.1

32.3

62.7

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.09

3.05

2.00

2.00

1.98

1.46

1.47

1.47

1.48

1.48

1.49

1.49

1.50

1.50

1.51

1.52

1.53

1.54

1.55

1.55

1.56

1.56

1.56

1.57

1.58

1.58

1.58

1.59

1.59

1.60

1.61

1.61

1.62

1.68

1.69

1.69

1.70

1.71

1.71

1.72

1.72

1.73

1.73

1.73

1.73

1.74

1.74

1.75

1.76

1.76

1.77

1.77

1.78

1.79

1.79

1.80

1.81

1.94

1.94

1.95

1.95

1.96

1.97

1.97

1.98

1.98

1.98

1.99

2.00

2.00

2.01

2.15

2.16

2.17

2.18

2.18

2.18

2.19

2.20

2.21

2.21

2.21

2.22

4.39

4.39

4.39

4.39

4.40

4.41

4.41

4.41

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

23.4

25.6

34.1

66.2

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.18

1.87

3.35

0.17

2.11

1.21

0.17

0.23

2.00

2.00

0.28

1.91

1.91

1.92

1.92

1.92

1.93

1.93

1.94

1.95

1.95

1.96

1.96

1.97

1.97

1.99

2.00

2.00

2.00

2.00

2.02

2.03

2.05

2.06

2.26

2.27

2.28

2.29

2.30

2.31

2.32

2.33

2.33

2.34

2.35

2.36

2.37

2.38

2.39

2.41

2.41

2.42

2.43

2.43

2.44

2.44

2.45

2.46

2.47

2.77

2.78

2.79

2.79

2.80

2.81

2.81

2.82

2.83

2.83

2.84

2.85

3.99

4.00

4.11

4.12

4.28

4.28

4.28

4.28

4.29

4.29

4.30

4.30

4.31

4.31

4.33

4.33

4.34

4.35

4.36

4.36

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

20.9

33.7

34.2

36.0

36.1

62.0

62.6

66.9

68.1

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

170.

9


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

10.2

2

2.24

3.33

0.11

0.19

1.97

2.01

0.20

6.93

4.60

1.06

1.99

2.00

2.01

2.03

2.04

2.06

2.08

2.09

2.10

2.20

2.21

2.22

2.23

2.24

2.26

2.27

2.28

2.30

2.31

2.33

2.34

2.36

2.37

2.62

2.64

2.65

2.66

2.66

2.68

2.68

2.69

2.71

3.56

3.57

3.69

3.70

4.27

4.28

4.28

4.29

4.30

4.36

4.37

4.38

4.38

4.39

7.26

7.37

7.38

7.38

7.39

7.39

7.41

7.42

7.42

7.43

7.43

7.44

7.44

7.45

7.45

7.45

7.63

7.63

7.63

7.64

7.64

7.65

7.65

7.65

7.66

7.66

7.67

7.67


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.3

26.8

26.9

35.7

35.9

36.8

37.7

62.3

63.4

66.2

67.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.7

127.7

129.

612

9.8

133.

313

3.6

135.

5


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

8.90

1.01

1.02

1.02

1.98

1.00

0.99

6.03

4.01

1.08

1.83

1.84

1.85

1.85

1.86

1.87

1.88

1.88

1.89

1.90

2.26

2.26

2.27

2.27

2.28

2.29

2.29

2.30

2.30

2.31

2.31

2.32

3.74

3.75

3.76

3.78

3.81

3.82

3.82

3.83

3.83

3.84

3.84

3.85

3.86

3.88

3.89

3.90

3.90

3.91

3.91

3.92

3.93

4.40

4.40

4.41

4.41

4.41

4.42

4.42

4.42

4.43

4.43

4.44

4.44

4.45

7.26

7.39

7.40

7.40

7.40

7.41

7.41

7.42

7.43

7.43

7.44

7.44

7.44

7.44

7.46

7.46

7.46

7.47

7.47

7.67

7.68

7.68

7.68

7.69

7.69

7.70

7.70

7.70

7.71

7.71


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.2

26.8

37.9

48.7

58.0

60.1

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.7

129.

713

3.3

133.

413

5.5

135.

5


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

5.91

5.92

2.97

3.00

1.00

0.97

1.93

1.93

1.93

5.91

1.35

1.41

1.63

1.64

1.66

1.67

1.68

1.69

1.70

1.71

1.71

1.73

1.74

1.76

1.79

1.80

1.81

1.82

1.83

1.84

1.85

1.86

1.86

1.87

1.88

1.89

1.90

1.91

1.92

2.04

2.05

2.06

2.07

2.08

2.09

2.10

2.10

2.11

2.15

2.15

2.18

2.18

2.19

2.19

2.20

2.20

2.20

2.21

2.22

2.22

2.23

3.53

3.55

3.56

3.58

3.63

3.64

3.65

3.66

3.66

3.67

3.68

3.76

3.77

3.77

3.78

3.78

3.79

3.79

3.80

4.04

4.05

4.05

4.06

4.07

4.07

4.08

4.09

4.10

4.10

4.11

4.12

4.13

4.14

4.16

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

25.6

25.6

26.9

29.8

30.2

31.1

31.7

48.0

48.1

60.7

61.0

69.2

69.3

75.0

75.6

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

109.

010

9.1


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.03

1.02

1.02

0.99

1.02

2.00

1.06

2.07

2.97

2.98

3.00

3.01

3.19

3.20

3.22

3.23

3.63

3.64

3.65

3.67

3.71

3.72

3.73

3.74

4.18

4.19

4.19

4.20

4.21

4.22

4.23

5.96

6.71

6.71

6.72

6.73

6.76

6.77

6.78


0102030405060708090100110120130140150160170180190200f1 (ppm)

40.6

47.3

61.0

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

101.

0

108.

310

9.8

122.

7

129.

8

146.

714

7.7


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.98

1.09

1.04

1.01

1.00

0.93

0.94

0.95

0.97

1.37

1.38

1.39

1.41

1.41

1.42

1.43

1.44

1.45

1.47

1.55

1.56

1.57

1.58

1.58

1.59

1.60

1.61

1.63

1.63

1.64

1.66

1.75

1.76

1.77

1.78

1.79

1.80

1.81

1.82

1.83

1.85

1.85

1.86

1.87

1.87

1.88

1.89

1.89

1.90

1.91

1.91

4.04

4.04

4.05

4.05

4.06

4.06

4.07

4.07

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

13.5

19.9

36.4

65.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.08

1.02

2.04

1.01

2.06

1.01

1.00

2.05

5.14

1.57

1.58

1.69

1.71

1.72

1.74

1.75

1.76

1.80

1.81

1.82

1.83

1.84

1.85

1.86

1.89

1.91

1.92

1.93

2.06

2.06

2.07

2.08

2.08

2.10

2.10

2.11

2.12

3.50

3.51

3.52

3.52

3.53

3.54

3.54

3.55

4.02

4.03

4.03

4.04

4.05

4.05

4.23

4.24

4.25

4.25

4.26

4.27

4.27

4.28

4.49

4.51

4.51

4.54

7.26

7.28

7.28

7.29

7.29

7.30

7.31

7.31

7.33

7.34

7.36

7.36

7.37


0102030405060708090100110120130140150160170180190200f1 (ppm)

20.8

26.9

30.9

60.0

66.1

69.4

72.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

612

7.6

128.

4

138.

3


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.93

2.18

1.04

1.00

2.04

0.96

0.99

2.02

5.08

1.61

1.63

1.70

1.71

1.72

1.73

1.74

1.76

1.77

1.78

1.78

1.80

1.80

1.81

1.82

1.83

1.84

1.85

1.90

1.91

1.92

1.93

1.93

1.94

1.95

1.95

1.96

1.96

1.97

1.98

2.12

2.12

2.13

2.14

2.14

2.15

2.15

2.16

2.17

2.18

2.18

3.48

3.49

3.50

3.51

3.52

3.53

3.53

3.54

3.55

3.56

3.96

3.96

3.97

3.98

3.98

3.99

4.00

4.09

4.10

4.11

4.13

4.14

4.49

4.51

4.52

4.54

7.26

7.27

7.28

7.28

7.29

7.30

7.30

7.31

7.33

7.34

7.36

7.36

7.37

7.37


0102030405060708090100110120130140150160170180190200f1 (ppm)

21.9

26.5

31.9

60.2

67.1

69.3

72.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

612

7.6

128.

4

138.

4


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

8.96

2.81

0.96

1.91

0.93

1.94

0.91

0.91

6.00

3.98

1.07

1.57

1.58

1.64

1.65

1.66

1.66

1.68

1.69

1.69

1.71

1.79

1.80

1.81

1.82

1.82

1.83

1.84

1.86

1.87

2.08

2.09

2.10

2.10

2.11

2.12

2.14

3.68

3.70

3.70

3.71

3.72

3.72

3.73

3.74

3.74

4.03

4.03

4.04

4.05

4.05

4.06

4.21

4.22

4.23

4.23

4.24

4.25

4.25

4.26

7.26

7.38

7.38

7.39

7.40

7.41

7.42

7.44

7.45

7.45

7.66

7.67

7.67

7.67

7.68

7.68


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.2

20.8

26.9

29.5

30.5

60.0

63.1

66.1

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.7

129.

613

3.8

133.

813

5.6


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.02

2.92

0.99

2.00

0.97

2.00

0.96

0.96

6.15

4.05

1.06

1.62

1.63

1.66

1.67

1.67

1.68

1.69

1.70

1.72

1.77

1.78

1.79

1.80

1.81

1.82

1.84

1.86

1.88

1.88

1.90

2.14

2.15

2.16

2.16

2.17

2.18

2.19

2.20

2.21

3.67

3.68

3.69

3.70

3.72

3.73

3.74

3.75

3.97

3.97

3.98

3.99

3.99

4.00

4.01

4.07

4.09

4.10

4.11

4.13

7.26

7.38

7.38

7.39

7.41

7.42

7.43

7.44

7.44

7.45

7.45

7.66

7.67

7.67

7.68

7.68

7.68


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.2

21.9

26.8

29.1

31.7

60.2

63.0

67.2

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

612

9.6

133.

713

3.8

135.

5


-3-2-10123456789101112f1 (ppm)

20.9

9

1.05

1.03

1.04

1.01

2.03

1.00

0.97

2.03

0.97

0.97

3.00

2.00

1.03

1.04

1.05

1.06

1.07

1.08

1.09

1.09

1.11

1.60

1.61

1.62

1.63

1.64

1.65

1.75

1.76

1.77

1.78

1.81

1.83

1.85

1.86

1.87

1.88

1.89

1.90

1.91

2.03

2.04

2.05

2.05

2.06

2.07

2.08

2.09

2.15

2.16

2.17

2.18

2.19

2.20

2.20

2.21

2.22

2.71

2.72

2.73

2.74

2.75

2.77

2.90

2.91

2.92

2.93

2.94

2.95

2.96

3.68

3.69

3.70

3.72

3.73

3.74

3.75

3.76

4.01

4.01

4.02

4.02

4.03

4.04

4.11

4.11

4.12

4.12

4.13

4.14

7.20

7.21

7.22

7.22

7.23

7.26

7.29

7.31

7.32


0102030405060708090100110120130140150160170180190200f1 (ppm)

12.0

18.0

29.9

31.4

32.7

36.2

62.6

64.6

65.5

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

212

8.5

128.

5

140.

5


-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

0.99

1.13

2.04

1.01

2.02

1.00

0.99

2.02

0.99

0.99

3.01

2.02

1.38

1.61

1.62

1.63

1.64

1.64

1.65

1.66

1.67

1.80

1.81

1.82

1.83

1.85

1.86

1.87

1.88

1.89

1.90

1.91

1.92

2.00

2.01

2.02

2.03

2.03

2.04

2.05

2.05

2.07

2.07

2.13

2.13

2.14

2.15

2.16

2.17

2.18

2.19

2.20

2.21

2.22

2.22

2.24

2.25

2.25

2.70

2.72

2.73

2.74

2.75

2.76

2.90

2.91

2.92

2.93

2.94

2.95

2.96

3.66

3.67

3.67

3.68

3.69

3.69

3.70

3.71

4.00

4.01

4.01

4.02

4.03

4.03

4.06

4.07

4.08

4.08

4.09

4.10

7.21

7.22

7.22

7.23

7.26

7.29

7.31

7.32


0102030405060708090100110120130140150160170180190200f1 (ppm)

29.7

31.1

32.6

36.0

62.1

64.5

65.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

212

8.5

128.

5

140.

4


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.07

3.07

1.02

1.02

1.03

1.01

3.08

1.00

1.25

1.26

1.28

1.58

1.60

1.99

2.00

2.01

2.01

2.02

2.03

2.03

2.04

2.05

2.05

2.06

2.07

2.25

2.25

2.26

2.27

2.27

2.28

2.29

2.30

2.31

2.31

2.46

2.48

2.50

2.51

2.53

2.56

2.57

2.58

2.59

2.60

2.61

2.61

2.62

4.09

4.09

4.10

4.11

4.11

4.12

4.14

4.15

4.16

4.23

4.24

4.25

4.25

4.26

4.27

4.27

4.28

7.26


-100102030405060708090100110120130140150160170180190200f1 (ppm)

14.2

20.8

29.2

31.1

59.8

60.6

65.1

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

172.

6


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.00

1.98

4.01

2.08

1.01

1.02

0.98

2.05

1.00

0.84

0.85

0.85

0.86

0.87

0.88

0.97

0.98

0.99

1.00

1.00

1.58

1.59

1.59

1.60

1.61

1.62

1.63

1.63

1.72

1.73

1.74

1.75

1.76

1.78

1.79

1.79

1.81

1.81

1.82

1.83

1.84

1.85

1.86

1.92

1.93

1.93

1.94

1.95

1.95

1.96

1.97

1.97

1.98

1.99

1.99

2.01

2.01

2.02

2.02

2.03

2.04

2.04

2.05

2.06

2.06

2.07

4.01

4.02

4.03

4.04

4.04

4.05

4.07

4.09

4.10

4.11

4.11

4.12

4.13

4.14

4.15

4.16

4.23

4.24

4.25

4.25

4.26

4.27

4.27

4.28

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

8.4

12.8

20.6

26.0

30.3

59.8

63.5

65.5

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

174.

8


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.98

1.00

1.00

1.00

0.98

2.00

2.02

2.01

1.00

0.97

5.31

1.56

1.58

1.68

1.69

1.70

1.70

1.71

1.71

1.72

1.73

1.83

1.84

1.85

1.85

1.87

1.87

1.89

1.91

1.93

1.94

1.96

1.97

2.05

2.06

2.07

2.08

2.09

2.10

2.88

2.91

2.91

2.94

3.69

3.70

3.72

3.72

3.73

3.74

3.75

3.77

3.87

3.89

3.89

3.90

3.90

3.91

3.92

4.00

4.01

4.02

4.02

4.03

4.04

4.21

4.21

4.22

4.23

4.23

4.24

4.25

4.25

7.21

7.22

7.23

7.25

7.26

7.28

7.28

7.29

7.29

7.30


0102030405060708090100110120130140150160170180190200f1 (ppm)

20.6

27.9

34.6

43.9

59.9

65.2

65.3

66.2

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

110.

8

126.

512

8.0

130.

5

136.

4


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.02

1.01

1.02

1.00

3.01

0.98

0.99

1.00

1.00

1.57

1.58

1.90

1.91

1.91

1.92

1.93

1.94

1.95

1.96

1.97

2.04

2.05

2.06

2.06

2.07

2.08

2.09

2.09

2.10

2.11

2.33

2.34

2.36

2.37

2.49

2.49

2.50

2.51

2.52

2.52

2.52

2.53

2.54

3.73

3.97

3.97

3.98

3.99

3.99

4.00

4.21

4.22

4.23

4.23

4.24

4.25

4.25

4.26

5.88

5.88

5.89

5.91

5.91

5.92

6.90

6.92

6.92

6.93

6.94

6.95

6.95

6.96


0102030405060708090100110120130140150160170180190200f1 (ppm)

20.5

29.1

31.9

51.5

59.7

64.8

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

122.

2

147.

0

166.

7


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

8.95

3.01

2.14

1.04

1.06

1.98

0.99

1.00

2.01

3.02

2.01

1.50

1.57

1.59

1.62

1.63

1.64

1.65

1.66

1.68

1.69

1.70

1.71

1.72

1.72

1.74

1.74

1.75

1.76

1.79

1.80

1.80

1.81

1.81

1.82

1.83

1.85

1.85

1.86

1.87

1.89

1.90

1.90

1.91

1.92

1.92

1.93

1.94

1.94

1.95

1.95

1.96

3.22

3.24

3.25

3.27

3.28

4.08

4.09

4.10

4.11

4.12

4.23

4.24

4.24

4.25

4.25

4.26

4.27

4.28

4.42

4.45

4.47

4.51

7.28

7.29

7.30

7.30

7.31

7.31

7.35

7.35

7.37

7.38

7.38


0102030405060708090100110120130140150160170180190200f1 (ppm)

0.8

CD3C

N1.

0 CD

3CN

1.2

CD3C

N1.

3 CD

3CN

1.5

CD3C

N1.

7 CD

3CN

1.8

CD3C

N

21.8

21.8

26.0

28.9

28.9

28.9

28.9

32.9

47.0

51.2

61.6

68.4

80.2

117.

9

128.

112

8.5

129.

5

140.

1

156.

6


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

2.02

2.01

2.00

0.99

0.99

2.02

2.02

1.60

1.61

1.77

1.79

1.81

1.83

1.84

1.86

1.99

2.01

2.02

2.03

2.04

2.04

2.06

3.72

3.73

3.74

3.97

3.97

3.98

4.00

4.00

4.05

4.06

4.07

4.09

4.10

7.26

7.70

7.71

7.71

7.72

7.72

7.73

7.83

7.83

7.84

7.84

7.85

7.85

7.86


0102030405060708090100110120130140150160170180190200f1 (ppm)

22.0

25.4

32.1

37.1

60.0

66.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

123.

3

132.

013

4.0

168.

3


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

2.91

9.09

1.19

1.14

1.07

1.11

1.00

1.01

1.02

1.00

6.18

4.03

0.96

0.97

0.99

1.07

1.43

1.44

1.45

1.47

1.49

1.50

1.51

1.53

1.53

1.54

1.55

1.56

1.56

1.57

1.57

1.57

1.58

1.59

1.60

1.60

1.61

1.63

1.78

1.79

1.80

1.80

1.81

1.82

1.82

1.83

1.84

1.85

1.89

1.90

1.90

1.91

1.92

1.93

1.94

1.95

1.96

3.82

3.83

3.84

3.85

3.96

3.98

3.98

4.00

4.05

4.06

4.06

4.07

4.07

4.08

4.08

4.46

4.46

4.47

4.47

4.47

4.48

4.49

4.49

7.26

7.38

7.39

7.39

7.40

7.42

7.44

7.44

7.45

7.47

7.47

7.47

7.65

7.65

7.67

7.67

7.67

7.69

7.69


0102030405060708090100110120130140150160170180190200f1 (ppm)

13.4

19.2

19.8

26.8

37.6

61.2

63.7

64.9

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

812

7.8

129.

913

2.7

133.

013

5.5

135.

6


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

3.05

9.19

1.06

0.99

0.99

0.99

1.00

2.00

0.99

6.34

4.10

0.95

0.96

0.98

1.08

1.42

1.43

1.44

1.44

1.45

1.46

1.46

1.47

1.48

1.49

1.49

1.62

1.63

1.64

1.64

1.65

1.66

1.67

1.68

1.69

1.69

1.74

1.75

1.76

1.77

1.78

1.79

1.80

1.81

1.82

1.91

1.91

1.92

1.93

1.93

1.94

1.94

1.95

1.95

1.95

1.96

1.97

1.97

3.89

3.91

3.92

3.93

4.07

4.08

4.08

4.09

4.09

4.10

4.34

4.34

4.35

4.36

4.36

4.37

4.38

7.26

7.39

7.39

7.40

7.41

7.42

7.44

7.44

7.44

7.45

7.46

7.46

7.47

7.47

7.47

7.69

7.69

7.69

7.70

7.70

7.71

7.71

7.71


0102030405060708090100110120130140150160170180190200f1 (ppm)

13.5

19.2

19.3

26.7

35.9

61.7

65.1

65.2

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

812

9.9

132.

813

2.9

135.

613

5.6


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

5.99

9.01

1.01

1.01

1.01

1.01

1.00

1.00

1.01

1.00

3.02

2.08

0.05

0.84

2.05

2.06

2.07

2.07

2.08

2.09

2.10

2.11

2.12

2.25

2.26

2.27

2.28

2.29

2.30

2.31

2.32

2.33

2.74

2.76

2.77

2.77

2.79

2.80

2.88

2.89

2.89

2.90

2.91

2.92

2.93

3.76

3.77

3.78

3.79

3.85

3.87

3.87

3.89

3.99

4.00

4.00

4.01

4.01

4.02

4.03

4.27

4.28

4.28

4.28

4.29

4.30

4.30

4.30

7.19

7.21

7.22

7.26

7.28

7.29

7.31


-100102030405060708090100110120130140150160170180190200f1 (ppm)

-5.5

-5.5

18.1

25.7

32.5

37.4

60.4

64.0

64.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

212

8.5

128.

5

140.

4


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.99

1.08

1.08

2.00

1.00

1.00

1.00

0.99

0.97

0.94

0.96

0.97

1.39

1.40

1.42

1.43

1.45

1.46

1.47

1.49

1.54

1.56

1.57

1.59

1.60

1.61

1.63

1.84

1.85

1.85

1.87

1.87

1.88

2.06

2.08

2.09

3.86

3.87

3.88

3.90

3.90

3.93

3.94

3.95

3.96

3.98

4.15

4.15

4.16

4.17

4.17

4.18

4.22

4.23

4.24

4.24

4.25

4.25

4.26

7.26


0102030405060708090100110120130140150160170180190200f1 (ppm)

13.4

19.8

37.2

61.7

64.5

65.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.02

0.14

1.00

1.12

0.14

2.00

2.01

0.06

3.23

2.11

2.14

2.16

2.17

2.18

2.19

2.20

2.21

2.22

2.23

2.24

2.25

2.26

2.27

2.28

2.68

2.69

2.70

2.73

2.75

2.76

2.77

2.79

2.90

2.90

2.91

2.92

2.93

2.94

2.95

2.96

3.69

3.70

3.71

3.85

3.86

3.87

3.88

3.89

3.90

3.92

3.93

3.94

3.95

4.14

4.14

4.15

4.17

4.18

4.18

4.19

4.20

4.20

4.21

5.79

5.80

5.82

7.22

7.23

7.25

7.26

7.31

7.32

7.34


0102030405060708090100110120130140150160170180190200f1 (ppm)

32.5

33.0

36.3

36.8

58.7

61.0

64.4

65.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

312

6.4

127.7

128.

512

8.6

128.

813

7.0

140.

214

0.3


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.01

2.01

0.06

0.99

1.03

0.05

2.00

2.00

0.02

3.12

2.01

2.06

2.07

2.08

2.09

2.14

2.15

2.16

2.17

2.18

2.19

2.20

2.21

2.23

2.23

2.24

2.25

2.26

2.27

2.53

2.69

2.70

2.73

2.74

2.75

2.76

2.77

2.79

2.90

2.91

2.92

2.93

2.94

2.95

2.96

3.70

3.85

3.86

3.87

3.89

3.90

3.91

3.92

3.93

3.94

3.96

4.14

4.14

4.15

4.16

4.17

4.17

4.18

4.19

4.19

4.20

4.21

5.80

7.22

7.23

7.23

7.25

7.26

7.30

7.32

7.33


0102030405060708090100110120130140150160170180190200f1 (ppm)

32.5

36.8

61.0

64.4

65.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

312

8.5

128.

6

140.

2


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.99

2.01

0.02

0.99

1.01

0.02

2.00

2.00

0.00

2.99

1.98

2.04

2.05

2.06

2.14

2.16

2.17

2.19

2.19

2.22

2.24

2.25

2.27

2.67

2.69

2.70

2.73

2.74

2.75

2.77

2.79

2.90

2.91

2.92

2.93

2.95

2.96

3.69

3.70

3.71

3.85

3.87

3.88

3.89

3.90

3.91

3.92

3.93

3.94

3.96

4.14

4.14

4.15

4.16

4.16

4.17

4.17

4.18

4.19

4.19

4.20

4.20

5.79

5.80

5.82

7.21

7.23

7.24

7.26

7.30

7.32

7.33


0102030405060708090100110120130140150160170f1 (ppm)

32.5

36.8

61.0

64.4

65.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

312

8.5

128.

6

140.

2


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.99

1.01

1.00

1.00

1.00

2.00

2.01

3.09

2.00

1.94

1.95

1.96

2.05

2.06

2.07

2.08

2.09

2.10

2.11

2.13

2.40

2.41

2.43

2.44

2.46

2.46

2.74

2.76

2.76

2.77

2.78

2.78

2.79

2.80

2.94

2.94

2.95

2.96

2.97

2.98

2.99

4.00

4.01

4.02

4.02

4.07

4.07

4.09

4.09

4.10

4.12

4.12

7.21

7.22

7.23

7.26

7.30

7.31

7.33


0102030405060708090100110120130140150160170180190200f1 (ppm)

31.8

36.6

60.8

64.4

66.3

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

126.

212

8.5

128.

5

140.

4


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.11

2.02

0.99

0.36

1.26

1.00

1.98

1.99

0.25

0.11

3.42

2.29

1.97

1.98

1.99

2.08

2.09

2.10

2.11

2.13

2.40

2.41

2.43

2.44

2.46

2.46

2.53

2.54

2.56

2.58

2.72

2.75

2.76

2.77

2.77

2.79

2.79

2.81

2.94

2.95

2.96

2.97

2.98

2.99

3.00

4.01

4.01

4.08

4.08

4.10

4.10

4.11

4.11

4.12

4.13

4.16

4.17

5.82

5.83

5.85

7.20

7.21

7.23

7.24

7.26

7.29

7.30

7.32

7.33


0102030405060708090100110120130140150160170180190200f1 (ppm)

29.7

31.8

34.4

36.6

60.8

64.4

66.3

66.8

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

124.

112

6.0

126.

212

6.2

128.

312

8.4

128.

512

8.5

133.

7

140.

414

1.1


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.25

1.00

2.63

4.71

2.16

1.00

1.05

2.70

2.70

2.04

12.1

4

2.20

2.21

2.22

2.23

2.24

2.26

2.27

3.76

3.77

3.78

3.79

3.79

3.81

3.83

3.85

3.85

3.86

3.87

3.88

3.90

3.91

3.92

3.93

3.93

3.95

3.97

3.97

3.98

3.99

4.00

4.00

4.01

4.02

4.03

4.03

4.04

4.05

4.06

4.28

4.29

4.30

4.31

4.31

4.34

4.35

4.36

4.36

4.37

4.38

4.38

4.39

4.39

4.40

4.40

4.41

4.42

4.42

4.43

4.43

4.44

4.45

4.59

4.62

4.63

4.65

7.26

7.30

7.32

7.33

7.35

7.36

7.37

7.39


0102030405060708090100110120130140150160170180190200f1 (ppm)

58.4

59.3

61.9

62.9

64.1

64.1

64.1

70.6

70.8

73.6

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.7

127.

812

7.9

128.

012

8.5

128.

513

7.2

137.

3


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.97

2.01

2.03

1.00

1.01

2.00

5.02

2.20

2.21

2.22

3.85

3.86

3.87

3.88

3.90

3.91

3.92

3.93

3.97

3.98

3.98

3.99

4.00

4.01

4.01

4.02

4.03

4.04

4.05

4.05

4.06

4.28

4.29

4.30

4.31

4.32

4.34

4.35

4.36

4.37

4.38

4.59

4.62

4.63

4.65

7.30

7.30

7.31

7.32

7.33

7.33

7.36

7.37

7.39


0102030405060708090100110120130140150160170180190200f1 (ppm)

59.3

62.9

64.2

70.9

73.6

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.7

127.

912

8.5

137.

3


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

11.5

8

2.00

0.54

0.54

3.08

0.24

3.15

1.97

7.95

5.15

1.05

1.51

1.53

1.53

1.55

1.57

1.78

1.79

1.80

1.82

1.90

1.90

1.93

1.93

1.99

2.00

2.02

2.03

2.03

2.04

2.05

2.05

2.06

2.06

2.07

2.08

2.09

2.11

2.12

2.13

2.29

2.31

2.32

2.34

2.36

3.45

3.48

3.49

3.51

3.59

3.61

7.26

7.36

7.36

7.37

7.37

7.38

7.40

7.42

7.42

7.43

7.44

7.44

7.45

7.63

7.63

7.65

7.66

7.66


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.3

19.3

26.8

26.9

29.8

30.7

35.3

38.1

57.1

58.6

65.7

69.5

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

127.

512

7.6

129.

512

9.6

133.

713

4.1

135.

5


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

5.00

1.41

2.00

0.23

0.30

1.02

1.11

0.34

3.84

2.48

1.06

1.99

2.00

2.01

2.02

2.06

2.07

2.08

2.10

2.20

2.22

2.23

2.24

2.25

2.27

2.28

2.30

2.31

2.34

2.36

2.62

2.63

2.64

2.66

2.68

2.69

2.70

3.56

3.57

3.68

3.70

4.27

4.28

4.29

4.36

4.37

4.38

7.26

7.37

7.39

7.40

7.42

7.42

7.43

7.45

7.62

7.63

7.64

7.65

7.65

7.66

7.67


0102030405060708090100110120130140150160170180190200f1 (ppm)

19.2

6

26.8

326

.88

35.7

235

.94

36.7

837

.69

62.3

163

.34

66.2

167

.92

76.7

4 CD

Cl3

77.0

0 CD

Cl3

77.2

5 CD

Cl3

127.

6512

7.74

129.

6412

9.77

133.

3313

3.64

135.

5313

5.54


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.16

2.59

1.18

1.20

0.79

1.11

2.00

0.37

0.54

6.10

3.98

1.05

1.06

1.58

1.60

1.61

1.62

1.64

1.65

1.66

1.76

1.77

1.79

1.80

1.81

2.04

2.13

2.14

2.16

2.17

2.47

2.49

2.50

3.65

3.66

3.67

3.69

3.70

5.55

5.56

5.58

5.63

5.64

5.65

5.67

7.17

7.26

7.37

7.39

7.40

7.42

7.43

7.45

7.65

7.66

7.66

7.66

7.67

7.67

7.68

7.68


0102030405060708090100110120130140150160170180190200f1 (ppm)

13.9

19.2

20.7

25.1

26.8

29.7

30.1

32.0

62.6

62.8

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

122.

512

7.3

127.

612

7.6

129.

612

9.6

133.

813

3.9

133.

913

5.5


-3-2-10123456789101112f1 (ppm)

9.33

0.96

1.72

1.19

1.31

0.87

1.14

2.00

0.42

0.55

6.34

4.14

1.05

1.06

1.61

1.63

1.64

1.66

1.67

1.69

1.69

1.70

1.70

1.77

1.79

1.80

1.81

1.81

1.83

2.06

2.06

2.23

2.24

2.26

2.27

2.43

2.44

2.46

3.66

3.66

3.67

3.67

3.68

3.68

5.39

5.39

5.41

5.41

5.42

5.42

5.48

5.49

5.51

5.52

7.26

7.37

7.37

7.38

7.40

7.41

7.42

7.42

7.43

7.43

7.44

7.44

7.65

7.66

7.67

7.67

7.68

7.69


0102030405060708090100110120130140150160170180190200f1 (ppm)

14.0

19.2

19.2

25.2

26.1

26.1

26.9

30.4

31.5

35.8

62.5

63.4

76.7

CDC

l377

.0 C

DCl3

77.3

CDC

l3

120.

112

5.4

127.

612

7.6

129.

512

9.5

133.

913

4.0

135.

213

5.5

135.

6


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SUEMENTARY INRMATIN - Nature Research · Electrospray Ionization (ESI+) spectra were performed using a time-of-flight (TOF) mass analyzer. Data are reported in the form of m/z (intensity