S 1

Supporting Information

SYNTHESIS OF A 3-THIOMANNOSIDE

María B. Comba, Alejandra G. Suárez, Ariel M. Sarotti, María I. Mangione* and Rolando A.

Spanevello and Enrique D. V. Giordano

Instituto de Química Rosario, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de

Rosario – CONICET. Suipacha 531, S2002RLK Rosario, Argentina.

Corresponding authors:

*spanevello@iquir-conicet.gov.ar and mangione@iquir-conicet.gov.ar

Table of contents

Experimental Section ..................................................................................................................................... S2

Synthesis of Allylic alcohol 4 ........................................................................................................................ S2

Synthesis of Allylic xanthate 5 ...................................................................................................................... S3

Synthesis of Diol 2 ........................................................................................................................................ S3

Synthesis of Thiocarbonate 6 ........................................................................................................................ S3

Synthesis of Disulfide 7 ................................................................................................................................. S4

Synthesis of Acetylated disulfide 8 ............................................................................................................... S4

Synthesis of Triacetate 11.............................................................................................................................. S4

Thiomannopyranoside 1 ................................................................................................................................ S5

Selected spectra ............................................................................................................................................... S6

Figure S-1: 1H-NMR (300 MHz) of compound 4 ......................................................................................... S6

Figure S-2: 13

C-NMR (75 MHz) of compound 4 .......................................................................................... S6

Figure S-3: 1H-NMR (300 MHz) of compound 5 ......................................................................................... S7

Figure S-4: 13

C-NMR (75 MHz) of compound 5 .......................................................................................... S7

Figure S-5: 1H-NMR (300 MHz) of compound 2 ......................................................................................... S8

Figure S-6: 13

C-NMR (75 MHz) of compound 2 .......................................................................................... S8

Figure S-7: 1H-NMR (300 MHz) of compound 6 ......................................................................................... S9

Figure S-8: 13

C-NMR (75 MHz) of compound 6 .......................................................................................... S9

Figure S-9: 1H-NMR (300 MHz) of compound 7 ....................................................................................... S10

Figure S-10: 13

C-NMR (75 MHz) of compound 7 ...................................................................................... S10

S 2

Figure S-11: 1H-NMR (300 MHz) of compound 8 ..................................................................................... S11

Figure S-12: 13

C-NMR (75 MHz) of compound 8 ...................................................................................... S11

Figure S-13: 1H-NMR (300 MHz) of compound 11 ................................................................................... S12

Figure S-14: 13

C-NMR (75 MHz) of compound 11 .................................................................................... S12

Figure S-15: 1H-NMR (300 MHz) of compound 1 ..................................................................................... S13

Figure S-16: 13

C-NMR (75 MHz) of compound 1 ...................................................................................... S13

Experimental Section

All reagents and solvents were used directly as purchased or purified according to standard procedures.

Analytical thin layer chromatography was carried out using commercial silica gel plates (Merck, Silica Gel 60

F254) and visualization was effected with short wavelength UV light (254 nm) and p-anysaldehyde solution

with subsequent heating. Flash column chromatography was performed with silica gel 60 H (Merck) using

EtOAc:hexanes mixtures. NMR spectra were recorded at 300 MHz for 1H, and 75 MHz for

13C on a Bruker

Avance-300 DPX spectrometer with CDCl3 as solvent and (CH3)4Si (1H) as internal standard. Chemical shifts

are reported in delta (δ) units in parts per million (ppm) and splitting patterns are designated as s, singlet; d,

doublet; t, triplet; q, quartet; and m, multiplet. Coupling constants are recorded in Hertz (Hz). The structure of

the products were determined by a combination of spectroscopic methods such as IR, 1D and 2D NMR

(including NOE, COSY, HSQC and HMBC experiments) and HRMS. Infrared spectra were recorded on a

Shimadzu IR Prestige-21 spectrometer using sodium chloride plate pellets. Absorbance frequencies are

recorded in reciprocal centimeters (cm–1

). High resolution mass spectra (HRMS) were obtained on a Bruker

microTOF-Q II LC-MS spectrometer. Optical rotations were determined using a JASCO DIP-1000 digital

polarimeter in 100 mm cells and the sodium D line (589 nm) at room temperature in the solvent and

concentration indicated. The melting points were taken on a Leitz Wetzlar Microscope Heating Stage Model

350 apparatus and are uncorrected. Levoglucosenone 3 was obtained according to the procedure previously

described.16

Synthesis of Allylic alcohol 4

Compound 3 (5.94 g, 47.13 mmoles) was dissolved in MeOH (32 mL) and cooled at 0 ºC.

CeCl3.7H2O (17.56 g, 47.13 mmoles) and NaBH4 (1.42 g, 37.7 mmoles) were added and

stirred for 2.5 h. The solution was neutralized with HCl 0.1 N to reach pH = 7. The mixture

was diluted with water (5 mL) and extracted several times with 50 mL portions of EtOAc.

The combined organic extracts were dried (Na2SO4) and concentrated. The residue was

purified by flash chromatography to afford 4 (5.59 g, 43.60 mmoles, 92%) as a white crystalline solid; Rf

(60% hexane- EtOAc) 0.17; .mp = 67-68 ºC (ethyl ether) [Lit 67-69 ºC]29

; [α]D25

-32.2 (c 0.995, CHCl3) [Lit -

34 (c 1.00, CHCl3)]29

; max (KBr) 3445 (OH), 3420, 1628 (C=C), 1122, 1066, 1045 cm-1

; H (300 MHz CDCl3)

6.12 (1H, dd, J 9.8, 4.3 Hz, H-4), 5.70 (1H, ddd, J 9.8, 2.4, 2.2 Hz, H-3), 5.51 (1H, dd, J 2.7, 2.2 Hz, H-1),

4.66 (1H, dd, J 4.3, 4.2 Hz, H-5), 4.33 (1H, s, H-2), 3.84 (1H, d, J 6.6 Hz, H-6endo), 3.75 (1H, dd, J 6.6, 4.2

Hz, H-6exo), 2.15 (1H, s, OH); C (75 MHz CDCl3) 130.6 (C-4), 129.0 (C-3), 101.1 (C-1), 71.1 (C-2), 70.5

(C-6), 68.6 (C-5).

S 3

Synthesis of Allylic xanthate 5

To a solution of compound 4 (1.26 g, 9.84 mmoles) in 10 mL of anhydrous THF

was added a suspension of NaH (60% dispersion in mineral oil) (0.86 g, 19.70

mmoles) in 40 mL of anhydrous THF. The mixture was cooled at 0 ºC. CS2 (1.5

mL, 24.60 mmoles) and CH3I (2.15 mL, 34.50 mmoles) were added. The mixture

was stirred during 3 h and then a solution of NH4Cl (sat) (2 mL) was added. The

solution was extracted with EtOAc (100 mL) and then washed with 5 mL of brine.

The combined organic extracts were dried (Na2SO4) and concentrated. The residue was purified by flash

chromatography to afford 5 (2.01 g, 9.22 mmoles, 94%) as a white crystalline solid; Rf (60% hexane- EtOAc)

0.56; mp = 61-62 ºC (diisopropylether). [α]D22

+18.2 (c 1.145, CHCl3); max (KBr) 3000, 2968, 2908, 1653

(C=C), 1288, 1208 (C=S), 1120, 882 cm-1

; H (300 MHz CDCl3) 6.36 (1H, s, H-2), 6.27 (1H, dd, J 9.8, 4.1

Hz, H-4), 5.79 (1H, s, H-1), 5.76 (1H, d, J 9.8 Hz, H-3), 4.73 (1H, dd, J 4.3, 4.1Hz, H-5), 4.02 (1H, d, J 6.4

Hz, H-6endo), 3.82 (1H, dd, J 6.4, 4.3 Hz, H-6exo), 2.59 (3H, s, SCH3); C (75 MHz CDCl3) 215.8 (C=S),

133.2 (C-4), 123.8 (C-3), 98.3 (C-1), 79.3 (C-2), 71.3 (C-5), 71.1 (C-6), 19.1 (SCH3); HRMS (EI, MH+) MH

+

found 219.01384, C8H11O3S2+ calcd 219.01441.

Synthesis of Diol 2

Compound 5 (795 mg, 3.64 mmoles) was dissolved in acetone:H2O 95:5

mixture (25.7 mL), NMO was added and then a solution of OsO4 in tBuOH was

added (9.20 mg, 0.04 mmoles). The mixture was stirred during 72 h and then

cooled at 0 ºC. Na2SO3 was added and after 10 min the solution was filtered.

The residue was purified by flash chromatography to afford 2 (861 mg, 3.42

mmoles, 94%) a white crystalline solid; Rf (60% Hexane-EtOAc) 0.08; mp =

119-120 ºC (diisopropylether); [α]D21

-155.6 (c 1.095, CHCl3); max (KBr) 3534

(OH), 3442 (OH), 2973, 2959, 2928, 2896, 1477, 1409, 1332, 1311, 1283, 1208 (C=S), 1088, 915cm-1

; H

(300 MHz CDCl3) 5.63 (1H, dd, J 8.3, 1.7 Hz, H-2), 5.60 (1H, d, J 1.7 Hz, H-1), 4.72 (1H, ddd, J 5.1, 1.9, 1.6

Hz, H-5), 4.09 (1H, s, H-3), 4.00 (1H, s, H-4), 3.86 (1H, dd, J 8.1, 5.1 Hz, H-6exo), 3.81 (1H, dd, J 8.1, 1.6

Hz, H-6endo), 3.06 (1H, s, OH), 3.02 (1H, s, OH), 2.60 (3H, s, SCH3); C (75 MHz CDCl3) 217.0 (C=S), 98.3

(C-1), 83.2 (C-2), 76.2 (C-5), 70.5 (C-3), 67.9 (C-4), 65.5 (C-6), 19.3 (SCH3); HRMS (EI MNa+) found

275.00115. C8H12O5S2Na+ calcd 275.00184.

Synthesis of Thiocarbonate 6

Xanthate 2 (190 mg, 0.75 mmoles) was dissolved in AcOH (12 mL) and cooled at 0 ºC

in an ice-bath. A solution of H2SO4/AcOH 50 % (7.8 mL) was added and the mixture

was stirred for 6 h at room temperature. The mixture was cooled to 0º C in an ice bath

and diluted with EtOAc (150 mL). Solid NaHCO3 (10 g) was added and after 10

minutes of stirring, the base was dissolved with water and the phases were separated.

The organic layer was washed with 5% aqueous NaHCO3 (2 x 50 mL), brine (50 mL)

and dried (Na2SO4 anh.). After filtration, the solvents were concentrated under reduced

pressure. The residue was purified by flash chromatography to afford compound 6 (124.3 mg, 0.50 mmoles,

67%) as white crystalline solid; Rf (60%, hexane:EtOAc) 0.21; []D23

-112.4 (c 1.1, CHCl3); max (KBr) 2981,

2843, 1748 (C=O), 1357, 1223, 1206, 1160, 1023, 841 cm−1

; H (300 MHz CDC13) 5.56 (1H, d, J 2.3 Hz, H-

1), 5.00 (1H, s, H-4), 4.69 (1H, dd, J 8.6, 2.3 Hz, H-2), 4.66 (1H, dd, J 5.8 Hz, H-5), 4.32 (1H, dd, J 8.6 Hz,

H-3), 4.30 (1H, dd, J 8.4 Hz, H-6endo), 3.88 (1H, dd, J 8.4 Hz, 5.8 Hz, H-6exo), 2.15 (3H, s, COCH3); C (75

MHz, CDCl3) 170.3 (C=O), 169.8 (COCH3), 98.0 (C-1), 74.4 (C-5), 74.2 (C-2), 69.8 (C-4), 66.1 (C-6), 45.3

(C-3), 20.8 (COCH3); HRMS (EI, MNa+): MNa

+, found 269.00921 C9H10O6SNa

+ calcd 269.00903.

S 4

Synthesis of Disulfide 7

Compound 6 (88 mg, 0.36 mmoles) was dissolved in anhydrous CH3OH

(12 mL) and anhydrous K2CO3 (86 mg, 0.62 mmoles) was added. The

mixture was stirred for 3 h at room temperature under argon atmosphere.

After completion (according to TLC analysis) the reaction mixture was

filtered over a Celite pad and washed with aliquots of CH3OH. The

combine filtrates were concentrated under reduced pressure obtaining

colorless oil. This compound was used without further purification in the next reaction step. For structural

characterization an aliquot of crude product 7 was suspended in methyl tert-butyl ether and stirred overnight

to obtain compound 7 as an off-white solid.; max (KBr) 3342 (OH), 2926, 1635, 1558, 1386, 1078 cm−1

; H

(300 MHz, H2O) 5.32 (1H, s, H-1), 4.55 (1H, d, J 5.1 Hz, H- 5), 4.43 (1H, d, J 8.1 Hz, H-6endo), 4.30 (1H, s,

H-4), 4.11 (1H, d, J 6.7 Hz, H-2), 3.66 (1H, dd, J 5.1, 7.7 Hz, H-6exo), 3.36 (1H, d, J 6.7 Hz, H-3), 3.27 (1H,

s, OH), 1.83 (1H, s, OH); C (75 MHz, H2O) 101.2 (C-1), 76.8 (C-5), 71.3 (C-4), 67.1 (C-2), 65.6 (C-6), 56.8

(C-3), HRMS (EI, MK+): MK

+, found 393.00692. C12H18KO8S2

+ calcd 393.00747.

Synthesis of Acetilated disulfide 8

Crude product 7 (88 mg) was dissolved in anhydrous CH2Cl2 (1.8 mL) and

the distilled pyridine (0.8 mL) was added at room temperature. Ac2O (0.4

mL, 3.57 mmoles) and DMAP (11 mg, 0.09 mmoles) were added and the

solution was stirred overnight under argon atmosphere. The mixture was

treated with HCl 50% (1 mL) and extracted with EtOAc (3 x 30 mL). The

combined organic layers were dried (Na2SO4 anh.) and concentrated under

reduce pressure. The resulting residue was purified by flash

chromatography to afford compound 8 (71 mg, 0.20 mmoles, 55% two steps) as a white crystalline solid.; 8:

Rf (60% hexane/ EtOAc) 0.32; []D28

+134.8 (c 1.1, CDCl3); mp 199 – 200º C (CH2Cl2/hexane); max (KBr)

1734 (C=O), 1375, 1361, 1247, 1236, 1153 cm−1

; H (300 MHz, CDCl3) 5.41 (1H, bs, H-1), 5.24 (1H, s, H-4),

4.88 (1H, dd, J 1.3, 7.0 Hz, H-2), 4.63 (1H, d, J 5.1 Hz, H-5), 4.49 (1H, d, J 8.0 Hz, H-6endo), 3.77 (1H, dd, J

5.1, 8.0 Hz, H-6exo), 3.59 (1H, d, J 7.0, 8.0 Hz, H-3), 2.17 (3H, s, COCH3), 2.08 (3H, s, COCH3); C (75

MHz, CDCl3) 170.2 (COCH3), 170.1 (COCH3), 99.6 (C-1), 75.1 (C-5), 72.4 (C-4), 70.4 (C-2), 65.9 (C-6),

48.6 (C-3), 21.1 (COCH3), 20.5 (COCH3); HRMS (EI, MNa+): MNa

+, found 545.07622. C20H26NaO12S2

+

calcd 545.07579.

Synthesis of Triacetate 11

Compound 8 (25 mg, 0.05 mmoles) was dissolved in anhydrous THF (6 mL) and

cooled to 0º C. LiAlH4 (18 mg, 0.50 mmoles) was added and the resulting suspension

was stirred at room temperature for 16 h. The mixture was cooled to 0º C, diluted with

EtOAc (2.5 mL) and the excess of reducing agent was destroyed by addition of

methanol (2.5 mL). Finally, the mixture was neutralized with AcOH and solvents were

concentrated under reduced pressure. The resulting residue was dissolved in anhydrous

pyridine (0.7 mL) and Ac2O (0.7 mL) and catalytic amount of DMAP was added. The

mixture was stirred for 16 h at room temperature. The reaction was concentrated and the residue was

dissolved in CH2Cl2 (20 mL) and washed with water (2 x 10 mL). The organic layer was dried (Na2SO4 anh.)

S 5

and the solvent was concentrated under reduced pressure. The residue was purified by flash chromatography

to give compound 11 (17.6 mg, 0.06 mmoles, 57% two steps) as a colorless oil; Rf (60% hexane/EtOAc) 0.39;

[]D26

-85.8 (c 0.6, CDCl3); max (liquid film) 1735 (C=O), 1691, 1373, 1217, 1062 cm−1

; H (300 MHz,

CDCl3) 5.45 (1H, s, H-1), 5.15 (1H, dd, J 1.6, 7.1 Hz, H-2), 4.86 (1H, bs, H-4), 4.57 (1H, d, J 5.4 Hz, H-5),

4.29 (1H, d, J 7.1 Hz, H-3), 4.27 (1H, d, J 8.4 Hz, H-6endo), 3.78 (1H, dd, J 5.4, 8.4 Hz, H-6exo), 2.35 (3H, s,

COCH3), 2.17 (3H, s, COCH3), 2.10 (3H, s, COCH3); C (75 MHz, CDCl3) 192.9 (COCH3), 168.8 (COCH3),

168.2 (COCH3), 98.8 (C-1), 73.7 (C-5), 73.1 (C-4), 67.5 (C-2), 64.9 (C-6), 41.1 (C-3), 29.2 (COCH3), 20.1

(COCH3), 19.6 (COCH3); HRMS (EI, MNa+): MNa

+, found 327.04975. C12H16NaO7S

+ calcd 327.05089.

Synthesis of Thiomannopyranoside 1

Compound 11 (55 mg, 0.18 mmoles) was dissolved in Ac2O (1.8 mL) under argon

atmosphere. The solution was cooled at 0 ºC and 2 drops of TMSOTf were added. The

mixture was stirred for 1 h at room temperature. Then, the reaction mixture was treated

with a saturated solution of NaHCO3 (1 mL) and extracted with EtOAc (3 x 10 mL).

The combine organic layers were dried (Na2SO4 anh.) and the solvent was concentrated

under reduce pressure. The residue was purified by flash chromatography to give 1

(57.6 mg, 0.16 mmoles, 88%) as a colorless oil; Rf (60% hexane/EtOAc) 0.6;

[a]D22

+28.4 (c 1.1, CDCl3); max (liquid film) 1749 (C=O), 1371, 1217 cm−1

; H (300 MHz, CDCl3) 6.01 (1H,

d, J 1.7 Hz, H-1), 5.17 (1H, dd, J 9.7, 11.4 Hz, H-4), 5.00 (1H, dd, J 1.7, 3.0 Hz, H-2), 4.26 (1H, dd, J 3.0,

11.4 Hz, H-3), 4.22 (1H, m, H-6), 4.08 (1H, m, H-5), 4.05 (1H, m, H-6), 2.31 (3H, s, COCH3), 2.17 (3H, s,

COCH3), 2.13 (3H, s, COCH3), 2.05 (3H, s, COCH3); 2.01 (3H, s, COCH3); C (75 MHz, CDCl3) 193.4

(COCH3), 170.6 (COCH3), 169.6 (2 COCH3), 168.2 (COCH3), 89.6 (C-1), 71.3 (C-5), 70.8 (C-2), 65.6 (C-4),

62.3 (C-6), 43.7 (C-3), 30.5 (COCH3), 20.9 (COCH3), 20.7 (COCH3), 20.6 (COCH3), 20.5 (COCH3); HRMS

(EI, MNa+): MNa

+, found 429.08385. C16H22NaO10S

+ calcd 429.08259.

S 6

Selected spectra

8 7 6 5 4 3 2 1 0 ppm2.07

2.08

2.10

3.73

3.75

3.76

3.77

3.83

3.85

4.33

4.64

4.66

4.67

5.51

5.52

5.52

5.69

5.69

5.70

5.72

5.73

5.73

6.09

6.11

6.12

6.14

1.13

1.04

1.02

0.99

1.00

0.98

0.99

1.00

H-4

H-3

H-1

H-5

H-

H-6

H-6

OH

CDCl3

TMS

Figure S-1: 1H spectrum of 4 in CDCl

3.

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

68.63

70.53

71.06

101.13

128.99

130.61

C-4 C-3 C-1

C-2 C-6

C-5

CDCl3

Figure S-2: 13

C spectrum of 4 in CDCl3.

S 7

8 7 6 5 4 3 2 1 0 ppm

2.59

3.81

3.83

3.83

3.84

4.01

4.03

4.72

4.73

4.74

5.73

5.74

5.75

5.76

5.77

5.78

5.79

5.79

6.24

6.25

6.25

6.26

6.26

6.26

6.28

6.28

6.28

6.29

6.29

6.29

6.36

3.09

1.05

1.05

1.00

1.97

1.01

0.97

H-4

H-3 H-1

H-5 H-2 H-6

H-6

SCH3

CDCl3

TMS

Figure S-3: 1H spectrum of 5 in CDCl

3.

200 180 160 140 120 100 80 60 40 20 0 ppm

19.130

71.143

71.281

79.261

98.248

123.757

133.161

215.804

C=S

C-3 C-1 C-5 C-6

SCH3 C-4

C-2

CDCl3

Figure S-4: 13

C spectrum of 5 in CDCl3.

S 8

8 7 6 5 4 3 2 1 0 ppm

2.60

3.02

3.07

3.83

3.83

3.84

3.86

4.01

4.08

4.09

4.09

4.11

4.72

4.73

4.73

5.61

5.61

5.62

5.65

5.65

2.90

1.85

2.05

0.98

1.03

1.00

1.91

H-4 H-3

H-1

H-5 H-2

H-6

OH

SCH3

CDCl3

TMS

Figure S-5: 1H spectrum of 2 in CDCl

3.

200 180 160 140 120 100 80 60 40 20 0 ppm

19.42

65.64

68.04

70.67

76.33

83.37

98.39

217.17

C=S

C-3

C-1 C-5

SCH3

C-4

C-2 C-6

CDCl3

Figure S-6: 13

C spectrum of 2 in CDCl3.

S 9

8 7 6 5 4 3 2 1 0 ppm2.15

3.86

3.88

3.89

3.91

4.30

4.30

4.30

4.31

4.32

4.33

4.33

4.34

4.66

4.68

4.69

4.71

4.71

5.00

5.56

5.56

3.24

1.06

2.09

2.06

1.04

1.00

H-3 H-4

COCH3

H-1

H-2 H-5

H-6 H-6 CDCl

3

TMS

Figure S-7: 1H spectrum of 6 in CDCl

3.

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

20.87

45.30

66.12

69.81

74.26

74.45

98.05

169.83

170.35

COCH3

COCH3

C-1 C-5 C-2 C-4

C-6 C-3

COCH3

CDCl3

Figure S-8: 13

C spectrum of 6 in CDCl3.

S 10

7 6 5 4 3 2 1 0 ppm

1.83

3.27

3.35

3.38

3.64

3.66

3.69

4.09

4.12

4.30

4.41

4.44

4.54

4.56

5.32

2.07

2.03

2.34

2.49

2.35

1.83

2.02

2.00

-OH

H-5

H-6

H-4

H-6

H-3 H-2

-OH

H-1

Figure S-9: 1H spectrum of 7 in D

2O.

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

56.80

65.63

67.14

71.31

76.81

101.19

C-1 C-5

C-4 C-2

C-6 C-3

Figure S-10: 13

C spectrum of 7 in D2O.

S 11

7 6 5 4 3 2 1 0 ppm2.08

2.16

3.58

3.61

3.74

3.76

3.77

3.79

4.48

4.50

4.60

4.62

4.86

4.87

4.89

4.89

5.23

5.41

6.42

6.20

2.05

2.05

2.02

2.02

2.04

1.97

2.00

H-1 H-4

H-2 H-5 H-6

H-6 H-3

COCH3

COCH3

CDCl

TMS

Figure S-11: 1H spectrum of 8 in CDCl

3.

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

20.48

21.14

48.57

65.92

70.42

72.39

75.07

99.56

170.09

170.18

C-1 C-4 C-5

C-2 C-6

C-3 COCH

3

COCH3

COCH3

COCH3

CDCl3

Figure S-12: 13

C spectrum of 8 in CDCl3.

S 12

7 6 5 4 3 2 1 0 ppm2.08

2.17

2.35

3.76

3.77

3.78

3.80

4.25

4.28

4.31

4.57

4.59

4.86

5.13

5.14

5.16

5.16

5.45

3.19

3.25

2.98

1.06

1.94

1.04

0.99

1.00

1.00

H-1

H-2

H-4

H-6 H-5

H-3 H-6

COCH3

COCH3

COCH3

CDCl3

Figure S-13: 1H spectrum of 11 in CDCl

3.

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

19.63

20.03

29.23

41.11

64.96

67.46

73.12

73.72

98.76

168.58

168.88

192.96

C-5 C-4 C-2

C-6 C-3

COCH3

COCH3 COCH

3

C-1 COCH

3

COCH3

COCH3

CDCl3

Figure S-14: 13

C spectrum of 11 in CDCl3.

S 13

7 6 5 4 3 2 1 0 ppm

2.01

2.05

2.13

2.17

2.31

4.00

4.01

4.05

4.10

4.20

4.22

4.22

4.23

4.24

4.26

4.27

4.99

5.00

5.00

5.01

5.14

5.17

5.18

5.21

6.01

6.01

3.10

3.20

2.98

3.11

3.22

2.18

2.20

1.01

1.05

1.00

H-1

H-2 H-4

H-5 H-6

H-3 H-6

COCH3

COCH3

COCH3

COCH3

COCH3

Figure S-15: 1H spectrum of 1 in CDCl

3.

CDCl3

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

20.56

20.65

20.68

20.87

30.51

43.65

62.34

64.85

70.76

71.33

89.59

168.16

169.58

170.61

193.41

C-1 C-5 C-2

C-6

C-3

COCH3

COCH3

COCH3

COCH3 C-4

COCH3

COCH3

COCH3

COCH3

COCH3

COCH3

Figure S-16: 13

C spectrum of 1 in CDCl3.

CDCl3