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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
Recommended