Catalyst-free efficient synthesis of 3-thio-2-deoxysugar derivatives in water

Article abstract of DOI:10.1080/07328300802120893

3-Thio- and 3-dithiocarbamoyl-2-deoxy carbohydrate derivatives have been synthesized using water as solvent without using a catalyst. In most of the cases yields obtained were excellent. Copyright Taylor & Francis Group, LLC.

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Catalyst‐free Efficient Synthesis of
3‐Thio‐2‐deoxysugar Derivatives in Water
Pintu Kumar Mandal a , Gour Hari Maiti b & Anup Kumar Misra a
a Medicinal and Process Chemistry Division, Central Drug Research Institute,
Lucknow, UP, India
b Department of Chemistry, Jadavpur University, Kolkata, India
Version of record first published: 27 Jun 2008.
To cite this article: Pintu Kumar Mandal , Gour Hari Maiti & Anup Kumar Misra (2008): Catalyst‐free Efficient
Synthesis of 3‐Thio‐2‐deoxysugar Derivatives in Water , Journal of Carbohydrate Chemistry, 27:4, 238-257
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Journal of Carbohydrate Chemistry, 27:238–257, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0732-8303 print 1532-2327 online
DOI: 10.1080/07328300802120893
Catalyst-free Efficient
Synthesis of 3-Thio-2-
deoxysugar Derivatives
in Water
1
Pintu Kumar Mandal, Gour Hari Maiti,2 and Anup Kumar Misra1
1Medicinal and Process Chemistry Division, Central Drug Research Institute,
Lucknow, UP, India
2Department of Chemistry, Jadavpur University, Kolkata, India
3-Thio- and 3-dithiocarbamoyl-2-deoxy carbohydrate derivatives have been synthesized
using water as solvent without using a catalyst. In most of the cases yields obtained
were excellent.
Keywords Carbohydrate, Deoxy sugars, Thia-Michael reaction, Dithiocarbamoyl,
Water, Catalyst free
INTRODUCTION
Thiosugars as potential therapeutics have attracted considerable attention of
medicinal chemists because of their ability to act as enzyme inhibitors.[1] Appli-
cation of thiosugars could be beneficial in designing therapeutics against infec-
tious disease and cancers.[2] Glycosyl dithiocarbamates could also serve as
potential enzyme inhibitors. In order to design carbohydrate-derived molecules
of medicinal interest, we were interested in synthesizing a series of 3-thio- or
3-dithiocarbamoyl-2-deoxy glycosides. Although a number of reports are avail-
able in the literature for the synthesis of thiosugars using thio-Michael
reaction of carbohydrate-derived thiols and activated alkenes,[3] synthesis of
dithiocarbamate derivatives are limited and none of them used carbohydrate
substrates.[4,5]
Received October 6, 2007; accepted April 10, 2008.
C.D.R.I. communication no. 7250.
Address correspondence to Anup Kumar Misra, Medicinal and Process Chemistry
Division, Central Drug Research Institute, Chattar Manzil Palace, Lucknow 226001,
UP, India. E-mail: akmisra69@rediffmail.com
238

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
239
Recently, two elegant reactionprotocols for the addition of thiols[6] and dithio-
carbamates[7] to the activated olefins in water without using catalyst were dis-
closed. Prompted by these reports, it has been envisaged that water-mediated
addition of a thiol or thiocarbamate anion generated in situ to the glycal-
derived 2,3-dideoxy-glyconolactol or lactone could result in 3-thio- or 3-thiocarba-
moyl-2-deoxy glyconolactol or lactones. Organic reactions in water instead of
using organic solvents have become attractive for environmental reasons. Here
we report an expedient synthesis of 3-mercapto or 3-dithiocarbamoyl-2-deoxy-
carbohydrate derivatives by the conjugate addition of thiols or dithiocarbamate
anion to glycal-derived a,b-unsaturated carbonyl compounds in water at rt
without the use of any catalyst. The reaction has been extended to a one-pot
preparation of 3-mercapto or 3-dithiocarbamoyl-2-deoxy-carbohydrate deriva-
tives starting from glycal derivatives (Sch. 1).
RESULTS AND DISCUSSION
In a set of initial experiments, 3,4,6-tri-O-acetyl-D-glucal (1 mmol) was taken in
water (5 mL) and stirred at 808C for 25 min to generate 4,6-di-O-acetyl-2,3-
dideoxy-erythro-hex-2-eno-pyranose following a literature method.[8] After
complete consumption of the starting material, the reaction mixture was
cooled to rt, thiophenol (1.1 mmol) was added, and the reaction mixture was
allowed to stir vigorously at rt. The reaction was completed in 5 min. The
crude product, isolated after workup, was acetylated using pyridine and acetic
anhydride to furnish 1,4,6-tri-O-acetyl-2-deoxy-3-mercaptophenyl-D-glucopyra-
nose in 90% yield. Variation of the amount of water did not show any significant
role in product formation. In order to establish the generality of the reaction,
3,4,6-tri-O-acetyl-D-glucal was treated with water as mentioned earlier and
the product obtained was allowed to react with a series of thiols in water at rt.
Excellent yields were obtained in each case within 5 to 15 min. Use of carbo-
hydrate-derived thiols instead of simple thiols also resulted in an excellent
yield of thio-linked disaccharides in a slightly longer reaction time (ꢀ30 min).
In order to prepare D-galactal-derived thio-adduct, 3,4,6-tri-O-acetyl-D-galactal
Scheme 1: Addition of thiols or dithiocarbamate anions to glycal-derived a,b-unsaturated
carbonyl compounds in water.

P. K. Mandal et al.
240
was first treated with water in the presence of a catalytic amount of mercuric
sulfate and sulfuric acid[9] for 5 min, the resulting solution was filtered, and
the filtrate was treated with a series of thiols as mentioned in the case of D-
glucal-derived 2,3-unsaturated lactol. In every case excellent yields of
3-mercapto-2-deoxy-D-galactose derivatives were obtained. This methodology
was then extended for the addition of thiols to a,b-unsaturated glyconolactones,
which are also prepared by the treatment of 3,4,6-tri-O-acetyl-glycals with a
combination of indium chloride and IBX in water.[10] A solution of 4,6-di-O-
acetyl-2,3-dideoxy-erythro-hex-2-eno-glyconolactone (1.0 mmol) and thiophenol
(1.2 mmol) in water (2 mL) was allowed to stir at rt. Excellent yield of 4,6-di-
O-acetyl-3-thiophenyl-2-deoxy-D-glyconolactone was achieved in 30 min. A
series of aryl and alkyl thiols and sugar-derived thiols were also allowed to
react with D-glucal- and D-galactal-derived 2,3-unsaturated glyconolactones to
furnish the products in very good yield (Table 1). Stirring plays a significant
role in the rate of reaction. In a control experiment, keeping a solution of D-
glucal-derived 2,3-unsaturated glyconolactol and thiophenol in water without
stirring at rt for 24 h furnished only a ꢀ40% yield of the product.
After achieving satisfactory yield of thia-Michael adducts of 2,3-unsatu-
rated glyconolactols and lactones, we turned our attention to the preparation
of 3-dithiocarbamoyl-2-deoxy sugar derivatives. For this purpose, we have
applied the reaction protocol reported by Saidi et al.[7] In a model experiment,
a suspension of piperidine (1 mmol) and carbon disulfide (1.2 mmol) in water
(5 mL) was allowed to stir at rt for 5 min. To the stirred reaction mixture was
added 4,6-di-O-acetyl-2,3-dideoxy-erythro-hex-2-enopyranose and the result-
ing reaction mixture was stirred at rt. Gratifyingly, the reaction was completed
in 1 h and the product was isolated by extracting the reaction mixture with
ethyl acetate. In order to generalize the reaction conditions, a series of
amines were allowed to react with D-glucal- and D-galactal-derived 2,3-unsatu-
rated aldehydes (or glyconolactols) in the presence of carbon disulfide in water
at rt. Excellent yields were achieved in every case (Table 1). All reactions can be
scaled up for the preparation of compounds in larger quantities. For spectral
analysis all products were conventionally acetylated using pyridine-acetic
anhydride and characterized by NMR and mass spectroscopy.
EXPERIMENTAL
General Methods
All the reactions were monitored by thin layer chromatography over silica
gel GF254 coated TLC plates. The spots on TLC were visualized by UV lamp and
warming ceric sulphate (2%Ce(SO4)2 in 2 N H2SO4) sprayed plates on a hot
plate. Silica gel 230–400 mesh was used for flash column chromatography.

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
241
Table 1: Addition of thiols and dithiocarbamate to a,b-unsaturated lactols and
lactones.
Time
(min)
Yield
(%)
Entry
Substrate
Thiol/dithiocarbamate
PhSH
2-(Me)-PhSH
3-(Me)-PhSH
4-(Me)PhSH
KSAc
R/Sa
1
2
3
4
5
6
5
5
5
5
10
15
90
85
95
90
92
88
1:3.5
1:4
1:3.5
1:4
1:2
1:4
HSCH2COOEt
7
30
80
1:6
8
9
10
11
12
2-Mercaptopyridine
Piperidine/CS2
Morpholine/CS2
Diethylamine/CS2
1,2,3,4-
15
60
60
60
90
82
78
75
80
72
1:4.5
1:6.6
1:9.6
1:6
1:9.5
Tetrahydroisoquinoline/CS2
PhSH
2-(Me)-PhSH
3-(Me)-PhSH
4-(Me)PhSH
13
14
15
16
17
18
5
5
5
5
15
15
92
88
95
95
90
85
4:1
4.5:1
3.6:1
4:1
2.5:1
4.6:1
KSAc
HSCH2COOEt
19
30
82
5:1
20
21
22
23
24
2-Mercaptopyridine
Piperidine/CS2
Morpholine/CS2
Diethylamine/CS2
1,2,3,4-
15
60
60
60
90
80
80
75
82
75
5:1
9.5:1
9.5:1
9.5:1
9.5:1
Tetrahydroisoquinoline/CS2
PhSH
2-(Me)-PhSH
3-(Me)-PhSH
4-(Me)PhSH
25
26
27
28
29
30
30
30
30
30
78
82
85
90
75
1:4
1:3.5
1:4
1:4
1:2.5
KSAc
30
30
72
0:1
31
32
33
34
PhSH
25
30
30
30
88
80
90
92
9:1
9.5:1
9.5:1
9.5:1
2-(Me)-PhSH
3-(Me)-PhSH
4-(Me)PhSH
35
30
82
1:0
aDetermined from the integration values of the corresponding signals in 1H NMR spectra.

P. K. Mandal et al.
242
1H and 13C NMR, 2D COSY, and HSQC spectra were recorded on a Brucker
Avance DPX 200 and 300 MHz using CDCl3 as solvent and TMS as internal
reference unless stated otherwise. Chemical shift values were expressed in
(ppm. ESI-MS spectra were recorded on a MICROMASS QUTTRO II triple
quadrupole mass spectrometer. Elementary analysis was carried out on a
Carlo ERBA-1108 analyzer. Optical rotations were measured at 258C on a
Rudolf Autopol III polarimeter. Commercially available grades of organic
solvents of adequate purity are used in many reactions.
General Experimental Condition
3-Mercapto-2-dideoxy-D-glycose
A solution of tri-O-acetyl-D-glucal (1 mmol) in distilled water (5 mL) was
placed on a preheated oil bath at 808C for 25 min. [In case of tri-O-acetyl-D-
galactal: to a solution of tri-O-acetyl-D-galactal (1 mmol) in water (5 mL) was
added catalytic amount of HgSO4 (5 mg) and 0.1 N H2SO4 (2–3 drops) and
the reaction mixture was stirred at rt for 5 min.] After consumption of the
starting glycal derivative (TLC), the reaction mixture was cooled to rt, appro-
priate thiol (1.2 mmol) was added to it, and the reaction mixture was stirred
vigorously for the appropriate time (Table 1). The reaction mixture was
extracted with EtOAc (20 mL). The organic layer was dried (Na2SO4) and con-
centrated under reduced pressure. The crude product was acetylated using
acetic anhydride and pyridine to furnish acetylated product, which was
purified by column chromatography using hexane-EtOAc to afford pure acetyl-
ated product. Following the similar reaction condition a series of 3-mercapto-2-
deoxy sugar derivatives and (1-3)-linked thiodisaccharides were synthesized.
3-Mercapto-2-deoxy-D-glyconolactone
To a solution of tri-O-acetyl-D-glucal (1 mmol) in distilled water (5 mL)
were added InCl3 (0.1 mmol) and IBX (2.5 mmol) and the reaction mixture
was allowed to stir at 808C for 6 h. After consumption of the starting
material (TLC) the reaction mixture was cooled to rt and extracted with
EtOAc (25 mL). The organic layer was washed with aq. NaHCO3, dried
(Na2SO4), and concentrated. To a solution of the crude lactone (1 mmol) in
water (5 mL) was added an appropriate thiol (1.2 mmol) and the reaction
mixture was stirred vigorously at rt for the appropriate time (Table 1). The
reaction mixture was extracted with EtOAc (20 mL). The organic layer was
dried (Na2SO4) and concentrated under reduced pressure. The crude product
was purified by column chromatography using hexane-EtOAc to furnish
pure product. Following the similar reaction condition a series of 3-mercapto-
2-deoxy glyconolactone derivatives were synthesized.

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
3-Dithiocarbamoyl-2-deoxy-D-glycose
243
To a solution of a secondary amine (1 mmol) in water (5 mL) was added
carbon disulfide (1.2 mmol) at rt and the reaction mixture was allowed to stir
at rt for 5 min. Glycal-derived 2,3-unsaturated glyconolactol was added to
the reaction mixture and the reaction mixture was allowed to stir at rt for
the appropriate time (Table 1). After completion (TLC), the reaction mixture
was extracted with EtOAc (25 mL). The organic layer was dried (Na2SO4)
and concentrated under reduced pressure. The crude product was acetylated
using acetic anhydride and pyridine and purified by column chromatography
using hexane-EtOAc (3:1) to furnish pure acetylated product, which was
characterized by NMR and mass spectral analysis. Following the similar
reaction condition a series of 3-dithiocarbamoyl-2-deoxy glyconolactol deriva-
tives were synthesized in excellent yield.
1,4,6-Tri-O-acetyl-3-mercaptophenyl-2-deoxy-a-D-glucopyranose (Table 1,
entry 1): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.49–7.28 (m, 5H, Ar-H), 6.20–6.06 (m, 1H,
H-1), 5.05–4.87 (m, 1H, H-4), 4.35–4.10 (m, 2H, H-3, H-6a), 4.08–3.90 (m, 2H,
H-5, H-6b), 2.12, 2.09, 2.07 (3 s, 9H, 3 COCH3), 2.16–1.87 (m, 2H, H-2ae); 13C
NMR (CDCl3, 50 MHz): d 170.7, 170.1, 169.9 (3 COCH3), 134.2–128.0 (Ar-C),
91.2 (C-1), 71.6 (C-5), 68.6 (C-4), 62.7 (C-6), 44.0 (C-3), 33.4 (C-2), 21.4, 21.3,
1
21.0 (3 COCH3); R-isomer: H NMR (CDCl3, 200 MHz): d 7.50–7.26 (m, 5H,
Ar-H), 6.15–6.02 (m, 1H, H-1), 5.0–4.84 (m, 1H, H-4), 4.40–4.18 (m, 2H,
H-3, H-6a), 4.10–3.95 (m, 1H, H-6b), 3.78–3.66 (m, 2H, H-5), 2.09, 2.07, 1.95
(3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.1, 169.6, 169.0 (3
COCH3), 134.3–128.0 (Ar-C), 92.8 (C-1), 75.7 (C-5), 69.0 (C-4), 62.7 (C-6),
47.0 (C-3), 35.7 (C-2), 21.2, 21.0, 20.9 (3 COCH3); ESI-MS: m/z ¼ 405.4
[M þ Na]þ; Anal. Calcd. for C18H22O7S (382.43): C, 56.53; H, 5.80; found: C,
56.35; H, 6.05.
1,4,6-Tri-O-acetyl-3-mercapto (2-methylphenyl)-2-deoxy-a-D-glucopyranose
(Table 1, entry 2): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.45–7.13 (m, 4H, Ar-H), 6.20–6.13 (m, 1H,
H-1), 5.0–4.90 (m, 1H, H-4), 4.45–4.20 (m, 1H, H-3), 3.88–4.10 (m, 2H, H-6ab),
3.68–3.50 (m, 1H, H-5), 2.40 (s, 3H, CH3), 2.18–1.90 (m, 2H, H-2ea), 2.11, 2.09,
2.06 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.8, 170.7, 169.9 (3
COCH3), 140.8–126.8 (Ar-C), 91.1 (C-1), 71.6 (C-5), 69.9 (C-4), 62.7 (C-6),
43.6 (C-3), 35.6 (C-2), 21.4, 21.3, 21.0 (3 s, 9H, 3 COCH3), 20.7 (CH3);
1
R-isomer: H NMR: d 7.45–7.13 (m, 4H, Ar-H), 6.18–6.12 (m, 1H, H-1), 5.02
(t, J ¼ 9.4 Hz, 1H, H-4), 4.40–4.18 (m, 1H, H-3), 4.15–4.0 (m, 2H, H-6ab),
3.40–3.28 (m, 1H, H-5), 2.42 (s, 3H, CH3), 2.20–1.90 (m, 2H, H-2ea), 2.09,
2.06, 2.03 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.1, 169.9,

P. K. Mandal et al.
244
169.0 (3 COCH3), 140.8–126.8 (Ar-C), 92.7 (C-1), 75.7 (C-5), 69.9 (C-4), 63.3
(C-6). 43.9 (C-3), 36.5 (C-2), 21.7, 21.4, 21.0, 20.8 (3 COCH3, CH3); ESI-MS:
m/z ¼ 419.5 [M þ Na]þ; Anal. Calcd. for C19H24O7S (396.45): C, 57.56; H,
6.10; found: C, 57.35; H, 6.35.
1,4,6-Tri-O-acetyl-3-mercapto (3-methylphenyl)-2-deoxy-a-D-glucopyranose
(Table 1, entry 3): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.26–7.08 (m, 4H, Ar-H), 6.15–6.10 (m, 1H,
H-1), 4.98–4.92 (m, 1H, H-4), 4.30–4.18 (m, 2H, H-3, H-6a), 4.0–3.98 (m, 2H,
H-5, H-6b), 2.35 (s, 3H, CH3), 2.12–1.87 (m, 2H, H-2ea), 2.08, 2.06 (2 s, 9H,
3 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.1 (2 C), 170.0 (3 COCH3),
138.7–127.6 (Ar-C), 90.5 (C-1), 71.2 (C-4), 68.0 (C-5), 62.7 (C-6), 43.2 (C-3),
35.0 (C-2), 21.1, 21.0, 20.8 (3 COCH3), 20.7 (CH3); R-isomer: 1H NMR
(CDCl3, 200 MHz): d 5.80–5.70 (m, 1H, H-1), 5.0–4.90 (m, 1H, H-4), 4.30–
4.20 (m, 2H, H-3, H-6a), 3.98–3.92 (m, 2H, H-5, H-6b), 2.33 (s, 3H, CH3),
2.12, 1.95, 1.93 (3 s, 9H, 3 COCH3), 2.10–1.85 (m, 2H, H-2ea); 13C NMR
(CDCl3, 50 MHz): d 169.3, 168.3 (2 C; 3 COCH3), 138.5–128.3 (Ar-C), 92.2 (C-
1), 75.2 (C-4), 68.5 (C-5), 62.1 (C-6), 43.9 (C-3), 33.6 (C-2), 20.9, 20.8, 20.5 (2
C) (3 COCH3, CH3); ESI-MS: m/z ¼ 419.5 [M þ Na]þ; Anal. Calcd. for
C19H24O7S (396.45): C, 57.56; H, 6.10; found: C, 57.32; H, 6.35.
1,4,6-Tri-O-acetyl-3-mercapto (4-methylphenyl)-2-deoxy-a-D-glucopyranose
(Table 1, entry 4): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.37–7.08 (m, 4H, Ar-H), 6.15–6.08 (m, 1H,
H-1), 5.0–4.85 (m, 1H, H-4), 4.30–4.07 (m, 2H, H-3, H-6a), 4.0–3.85 (m, 2H,
H-5, H-6b), 2.35 (s, 3H, CH3), 2.10–1.80 (m, 2H, H-2ea), 2.08, 2.06 (2 s, 9H,
3 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.3, 170.2, 169.6 (3 COCH3),
138.3–129.7 (Ar-C), 90.9 (C-1), 71.3 (C-5), 69.1 (C-4), 62.3 (C-6), 43.6 (C-3),
35.1 (C-2), 20.9 (CH3), 20.6, 20.5, 20.4 (3 COCH3); R-isomer: 1H NMR
(CDCl3, 200 MHz): d 7.37–7.08 (m, 4H, Ar-H), 5.77–5.65 (m, 1H, H-1), 5.02–
4.88 (m, 1H, H-4), 4.30–4.10 (m, 2H, H-3, H-6a), 4.02–3.85 (m, 2H, H-6b),
2.31 (s, 3H, CH3), 2.11, 2.06, 2.00 (3 s, 9H, 3 COCH3), 2.10–1.82 (m, 2H,
H-2ea); 13C NMR (CDCl3, 50 MHz): d 169.6, 169.3, 168.5 (3 COCH3), 138.3–
127.4 (Ar-C), 92.4 (C-1), 75.4 (C-4), 68.2 (C-5), 62.3 (C-6), 44.7 (C-3), 33.7 (C-
2), 21.1, 21.0, 20.9 (2 C) (3 COCH3, CH3); ESI-MS: m/z ¼ 419.5 [M þ Na]þ;
Anal. Calcd. for C19H24O7S (396.45): C, 57.56; H, 6.10; found: C, 57.35; H, 6.38.
1,4,6-Tri-O-acetyl-3-mercaptoacetyl-2-deoxy-a-D-glucopyranose (Table 1,
entry 5): S-isomer
1H NMR (CDCl3, 200 MHz): d 6.18–6.10 (m, 1H, H-1), 6.05.92 (m, 1H, H-4),
5.0–4.85 (m, 1H, H-3), 4.30–4.0 (m, 3H, H-5, H-6ab), 2.33 (s, 3H, SCOCH3),
2.18–2.0 (m, 2H, H-2ea), 2.11, 2.07, 2.03 (3 s, 9H, 3 COCH3); 13C NMR
(CDCl3, 50 MHz): d 192.9 (SCOCH3), 169.8, 169.0, 168.8 (3 COCH3), 90.6

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
245
(C-1), 72.8 (C-5), 66.5 (C-4), 61.7 (C-6), 39.5 (C-3), 32.4 (C-2), 20.8 (2 C), 20.7
(2 C) (3 COCH3, SCOCH3); R-isomer: 1H NMR (CDCl3, 200 MHz): d
6.15–6.08 (m, 1H, H-1), 5.88–5.78 (m, 1H, H-4), 5.05–4.92 (m, 1H, H-3),
4.32–4.05 (m, 3H, H-5, H-6ab), 2.36 (s, 3H, SCOCH3), 2.20, 2.15, 2.09 (3 s,
9H, 3 COCH3), 2.18–2.0 (m, 2H, H-2ea); 13C NMR (CDCl3, 50 MHz): d 193.7
(SCOCH3), 169.0, 168.0, 168.0 (3 COCH3), 91.6 (C-1), 74.9 (C-5), 67.5 (C-4),
62.5 (C-6), 38.2 (C-3), 33.0 (C-2), 21.0, 20.9, 20.8 (2 C); ESI-MS: m/z ¼ 371.4
[M þ Na]þ; Anal. Calcd. for C14H20O8S (348.37): C, 48.27; H, 5.79; found: C,
48.05; H, 6.0.
1,4,6-Tri-O-acetyl-3-(ethylglycoloyl)mercapto-2,3-dideoxy-a-D-glucopyranose
(Table 1, entry 6): S-isomer
1H NMR (CDCl3, 200 MHz): d 6.10–6.08 (m, 1H, H-1), 4.80 (t, J ¼ 9.6 Hz,
1H, H-4), 4.28–4.21 (m, 4H, H-6ab, OCH2CH3), 4.04–3.98 (m, 1H, H-3),
3.65–3.58 (m, 1H, H-5), 3.34–3.23 (m, 2H, SCH2COOEt), 2.22–2.15 (m, 1H,
H-2e), 2.11, 2.09, 2.08 (3 s, 9H, 3 COCH3), 2.01–1.85 (m, 1H, H-2a), 1.30
(t, J ¼ 7.5 Hz, 1H, CH2CH3); 13C NMR (CDCl3, 50 MHz): d 170.2 (COOEt),
169.3, 169.2, 168.5 (3 COCH3), 92.2 (C-1), 72.9 (C-5), 67.2 (C-4), 63.0
(COOCH2CH3), 61.3 (C-6), 44.2 (C-3), 36.2 (SCH2COOEt), 32.5 (C-2), 21.0,
20.8, 20.7 (3 COCH3), 14.1 (CH2CH3); R-isomer: 1H NMR (CDCl3,
200 MHz): d 6.17–6.10 (m, 1H, H-1), 4.91 (t, J ¼ 9.4 Hz, 1H, H-4), 4.28–4.14
(m, 4H, H-6ab, OCH2CH3), 3.99–3.94 (m, 1H, H-3), 3.73–3.66 (m, 1H, H-5),
3.26–3.15 (m, 2H, SCH2COOEt), 2.31–2.20 (m, 1H, H-2e), 2.12, 2.09, 2.08 (3
s, 9H, 3 COCH3), 2.0–1.80 (m, 1H, H-2a), 1.30 (t, J ¼ 7.4 Hz, 3H,
COOCH2CH3); 13C NMR (CDCl3, 50 MHz): d 170.2, 169.7, 169.5, 169.3
(COOEt, 3 COCH3), 90.7 (C-1), 71.4 (C-5), 68.4 (C-4), 62.2 (COOCH2CH3),
61.3 (C-6), 41.4 (C-3), 35.5 (SCH2COOEt), 31.7 (C-2), 20.9, 20.7, 20.6 (3
COCH3), 14.1 (CH2CH3); ESI-MS: m/z ¼ 415.4 [M þ Na]þ; Anal. Calcd. for
C16H24O9S (392.42): C, 48.97; H, 6.16; found: C, 48.75; H, 6.35.
1,4,6-Tri-O-acetyl-3-mercapto (2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2-
deoxy-a-D-glucopyranose (Table 1, entry 7): S-isomer
1H NMR (CDCl3, 300 MHz): d 5.23 (t, J ¼ 9.9 Hz, 1H, H-30), 5.14
(t, J ¼ 9.9 Hz, 1H, H-20), 4.98 (t, J ¼ 9.6 Hz, 1H, H-40), 4.93–4.87 (m, 1H,
H-4), 4.70–4.65 (m, 1H, H-1), 4.54 (d, J ¼ 9.9 Hz, 1H, H-10), 4.50–4.36 (m,
1H, H-3), 4.31–3.98 (m, 4H, H-6ab, H-6a0 b), 3.74–3.70 (m, 2H, H-5, H-50),
2.39–2.12 (m, 2H, H-2ea), 2.13, 2.12, 2.11, 2.10, 2.08, 2.07, 2.02 (7 s, 21H, 7
COCH3); 13C NMR (CDCl3, 75 MHz): d 170.1, 169.9, 169.5, 169.2, 168.9,
168.7, 168.4 (7 COCH3), 90.3 (C-1), 82.6 (C-10), 75.4, 73.4, 69.6, 67.9 (2 C),
66.5, 62.7 (C-6), 61.8 (C-60), 40.8 (C-3), 36.6 (C-2), 20.7 (2 C), 20.6 (2 C), 20.5
1
(2 C), 20.3; R-isomer: H NMR (CDCl3, 300 MHz): d 5.20 (t, J ¼ 9.9 Hz, 1H,
H -30), 5.15 (t, J ¼ 9.9 Hz, 1H, H-20), 5.0 (t, J ¼ 9.6 Hz, 1H, H-40), 4.90–4.82
(m, 1H, H-4), 4.72–4.68 (m, 1H, H-1), 4.60 (d, J ¼ 9.9 Hz, 1H, H-10),

P. K. Mandal et al.
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4.48–4.38 (m, 1H, H-3), 4.30–4.0 (m, 4H, H-6ab, H-6a0 b), 3.90–3.82 (m, 2H, H-5,
H-50), 2.40–2.15 (m, 2H, H-2ea), 2.14, 2.12, 2.11, 2.09, 2.07, 2.06, 2.0 (7 s, 21H, 7
COCH3); 13C NMR (CDCl3, 75 MHz): d 170.4, 170.0, 169.5, 169.3, 168.9,
168.7, 168.4 (7 COCH3), 90.7 (C-1), 83.7 (C-10), 75.7, 73.5, 69.6, 67.7, 67.4,
66.7, 61.6 (C-6), 61.1 (C-60), 37.3 (C-3), 33.5 (C-2), 20.9 (2 C), 20.7 (2 C), 20.6
(2 C), 20.5; ESI-MS: m/z ¼ 659.6 [M þ Na]þ; Anal. Calcd. for C26H36O16S
(636.62): C, 49.05; H, 5.70; found: C, 48.80; H, 6.0.
1,4,6-Tri-O-acetyl-3-mercapto (2-pyridyl)-2-deoxy-a-D-glucopyranose (Table 1,
entry 8): S-isomer
1H NMR (CDCl3, 200 MHz): d 8.43–8.37 (m, 1H, Ar-H), 7.51–7.43 (m, 1H,
Ar-H), 7.17–6.96 (m, 2H, Ar-H), 6.20–6.17 (m, 1H, H-1), 5.17–5.10 (m, 2H,
H-3, H-4), 4.39–4.19 (m, 2H, H-6ab), 4.10–4.0 (m, 1H, H-5), 2.35–2.0 (m, 2H,
H-2ea), 2.18, 2.14, 2.10 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 50 MHz): d
170.2, 170.1, 169.3 (3 COCH3), 157.1–119.6 (Ar-C), 90.9 (C-1), 73.0 (C-5),
67.7 (C-4), 62.2 (C-6), 37.5 (C-3), 32.6 (C-2), 20.9, 20.8 (2 C) (3 COCH3);
1
R-isomer: H NMR (CDCl3, 200 MHz): d 8.43–8.37 (m, 1H, Ar-H), 7.51–7.43
(m, 1H, Ar-H), 7.17–6.96 (m, 2H, Ar-H), 6.10–6.0 (m, 1H, H-1), 5.17–5.08
(m, 1H, H-4), 5.0–4.90 (m, 1H, H-3), 4.40–4.20 (m, 2H, H-6ab), 4.08–4.0
(m, 1H, H-5), 2.30–1.95 (m, 2H, H-2ea), 2.10, 1.90, 1.87 (3 s, 9H, 3 COCH3);
13C NMR (CDCl3, 50 MHz): d 169.3, 169.1, 168.3 (3 COCH3), 157.1–119.6
(Ar-C), 90.7 (C-1), 75.3 (C-4), 67.7 (C-5), 62.1 (C-6), 38.1 (C-3), 33.5 (C-2),
21.1, 20.9, 20.5 (3 COCH3); ESI-MS: m/z ¼ 406.4 [M þ Na]þ; Anal. Calcd. for
C17H21NO7S (383.82): C, 53.25; H, 5.52; found: C, 53.02; H, 5.75.
1,4,6-Tri-O-acetyl-3-(N-piperidinodithiocarbamoyl)-2-deoxy-a-D-
glucopyranose (Table 1, entry 9): S-isomer
1H NMR (CDCl3, 200 MHz): d 6.18–6.15 (m, 1H, H-1), 5.32–5.23 (m, 1H,
H-4), 4.82–4.68 (m, 1H, H-3), 4.55–4.0 (m, 5H, H-5, H-6ab, NCH2), 3.93–3.82
(m, 2H, NCH2), 2.70–2.57 (m, 1H, H-2e), 2.02–1.87 (m, 1H, H-2a), 2.11, 2.09,
2.06 (3 s, 9H, 3 COCH3), 1.80–1.62 (m, 6H, 3-CH2-); 13C NMR (CDCl3,
50 MHz): d 192.5 (CS), 170.5, 170.3, 168.9 (3 COCH3), 91.1 (C-1), 71.8 (C-4),
66.8 (C-5), 62.2 (C-6), 52.9 (CH2), 51.5 (CH2), 48.1 (C-3), 35.9 (C-2), 25.4
(CH2), 24.2 (2 C, CH2), 21.1, 21.0, 20.9 (3 COCH3); R-isomer: 1H NMR
(CDCl3, 200 MHz): d 6.47–6.36 (m, 1H, H-1), 5.20–5.10 (m, 1H, H-4), 5.02–
4.94 (m, 1H, H-3), 4.50–4.0 (m, 5H, H-5, H-6ab, NCH2), 2.96–2.80 (m, 1H,
H-2e), 2.42–2.20 (m, 1H, H-2a), 2.12, 2.09, 2.06 (3 s, 9H, 3 COCH3), 1.78–
1.60 (m, 6H, 3 CH2-); 13C NMR (CDCl3, 50 MHz): d 192.4 (CS), 169.8, 169.6,
168.6 (3 COCH3), 91.5 (C-1), 71.0 (C-4), 68.1 (C-5), 62.6 (C-6), 53.0 (CH2),
51.5 (CH2), 49.1 (C-3), 39.5 (C-2), 25.4 (CH2), 24.2 (2 C, CH2), 21.0, 20.9, 20.8
(3 COCH3); ESI-MS: m/z ¼ 456.5 [M þ Na]þ; Anal. Calcd. for C18H27NO7S2
(433.54): C, 49.87; H, 6.28; found: C, 49.64; H, 6.55.

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
1,4,6-Tri-O-acetyl-3-(N-morpholinodithiocarbamoyl)-2-deoxy-a-D-
247
glucopyranose (Table 1, entry 10): S-isomer
1H NMR (CDCl3, 200 MHz): d 6.18–6.13 (m, 1H, H-1), 5.14–5.04 (m, 1H,
H-4), 4.74–4.64 (m, 1H, H-3), 4.52–4.02 (m, 7H, H-5, H-6ab, N(CH2-)2), 3.84–
3.66 (m, 4H, 2 OCH2), 2.65–2.53 (m, 1H, H-2e), 2.12, 2.10, 2.08 (3 s, 9H,
3 COCH3), 1.97–1.82 (m, 1H, H-2a); 13C NMR (CDCl3, 50 MHz): d 194.5 (CS),
170.3, 169.6, 168.7 (3 COCH3), 91.0 (C-1), 71.8 (C-4), 66.5 (C-5), 66.0 (2 C, 2
OCH2), 62.1 (C-6), 50.4 (2 C, 2 NCH2), 48.2 (C-3), 35.9 (C-2), 21.0, 20.9, 20.7
(3 COCH3); ESI-MS: m/z ¼ 458.5 [M þ Na]þ; Anal. Calcd. for C17H25NO8S2
(435.51): C, 46.88; H, 5.79; found: C, 46.66; H, 6.0.
1,4,6-Tri-O-acetyl-3-(N,N-diethylaminodithiocarbamoyl)-2-deoxy-a-D-
glucopyranose (Table 1, entry 11): S-isomer
1H NMR (CDCl3, 200 MHz): d 6.17–6.11 (m, 1H, H-1), 5.29–5.25 (m, 1H,
H-4), 4.80–4.65 (m, 1H, H-3), 4.52–4.26 (m, 1H, H-6a), 4.08–3.95 (m, 4H,
2 NCH2CH3), 3.77–3.70 (m, 2H, H-5, H-6b), 2.62–2.55 (m, 1H, H-2e), 2.37–
2.29 (m, 1H, H-2a), 2.14, 2.10, 2.05 (3 s, 9H, 3 COCH3), 1.38–1.26 (m, 6H, 2
NCH2CH3); 13C NMR (CDCl3, 50 MHz): d 192.4 (CS), 170.4, 170.3, 169.6 (3
COCH3), 91.5 (C-1), 74.0 (C-4), 66.8 (C-5), 62.5 (C-6), 46.5 (2 C, 2 CH2CH3),
44.4 (C-3), 31.4 (C-2), 21.2, 20.8, 20.6 (3 COCH3), 12.8, 12.5 (2 CH2CH3);
1
R-isomer: H NMR (CDCl3, 200 MHz): d 6.14–6.10 (m, 1H, H-1), 5.20–5.10
(m, 1H, H-4), 5.0–4.92 (m, 1H, H-3), 4.56–4.36 (m, 1H, H-6a), 4.28–4.15
(m, 4H, 2 NCH2CH3), 3.95–3.88 (m, 2H, H-5, H-6b), 2.95–2.77 (m, 1H, H-2e),
2.30–2.0 (m, 1H, H-2a), 2.14, 2.10, 2.08 (3 s, 9H, 3 COCH3), 1.35–1.24
(m, 6H, 2 CH2CH3); 13C NMR (CDCl3, 50 MHz): d 192.6 (CS), 169.0, 168.9,
168.4 (3 COCH3), 90.7 (C-1), 75.4 (C-4), 69.6 (C-5), 62.2 (C-6), 49.5 (2 C, 2
CH2CH3), 46.7 (C-3), 31.4 (C-2), 21.2, 21.1, 20.8 (3 COCH3), 12.9, 12.6
(2 CH2CH3); ESI-MS: m/z ¼ 444.5 [M þ Na]þ; Anal. Calcd. for C17H27NO7S2
(421.53): C, 48.44; H, 6.46; found: C, 48.20; H, 6.62.
1,4,6-Tri-O-acetyl-3-(1,2,3,4-tetrahydroisoquinolinodithiocarbamoyl)-2-
dideoxy-a-D-glucopyranose (Table 1, entry 12): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.29–7.21 (m, 4H, Ar-H), 6.18–6.12 (m, 1H,
H-1), 5.36–5.24 (m, 1H, H-4), 5.15–4.95 (m, 1H, H-3), 4.60–4.30 (m, 3H, H-5,
H-6ab), 4.26–4.18 (m, 2H, NCH2CH2-), 4.14–4.0 (m, 2H, NCH2CH2-), 3.04–3.0
(m, 2H, NCH2), 2.69–2.56 (m, 1H, H-2e), 2.44–2.27 (m, 1H, H-2a), 2.10, 2.08,
2.05 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 50 MHz): d 193.3 (CS), 170.4,
170.3, 169.5 (3 COCH3), 134.1–126.1 (Ar-C), 91.1 (C-1), 74.0 (C-4), 71.7 (C-5),
62.1 (C-6), 53.7 (NCH2CH2-), 50.1 (NCH2CH2-), 48.0 (C-3), 35.8 (C-2), 28.9
(NCH2), 21.2, 21.0, 20.7 (3 COCH3); ESI-MS: m/z ¼ 504.6 [M þ Na]þ; Anal.
Calcd. for C22H27NO7S2 (481.58): C, 54.87; H, 5.65; found: C, 54.64; H, 6.87.

P. K. Mandal et al.
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1,4,6-Tri-O-acetyl-3-mercaptophenyl-2-deoxy-a-D-galactopyranose (Table 1,
entry 13): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.48–7.30 (m, 5H, Ar-H), 6.46–6.44 (m, 1H,
H-1), 5.58–5.52 (m, 1H, H-4), 5.30–5.20 (m, 1H, H-3), 4.40–4.10 (m, 2H,
H-6ab), 4.0–3.86 (m, 1H, H-5), 2.18–2.0 (m, 2H, H-2ea), 2.09, 2.03 (2 s); 13C
NMR (CDCl3, 50 MHz): d 170.7, 170.4, 170.3 (3 COCH3), 145.7–128.6 (Ar-C),
91.6 (C-1), 73.1 (C-5), 64.3 (C-4), 62.2 (C-6), 44.6 (C-3), 30.9 (C-2), 21.4, 21.1,
1
21.0 (3 COCH3); S-isomer: H NMR (CDCl3, 200 MHz): d 7.48–7.30 (m, 5H,
Ar-H), 6.20–6.12 (m, 1H, H-1), 5.30–5.22 (m, 1H, H-4), 4.73–4.68 (m, 1H,
H-3), 4.38–4.10 (m, 2H, H-6ab), 3.50–3.42 (m, 1H, H-3), 2.18–2.0 (m, 2H,
H-2ea), 2.10, 2.05, 2.03 (3 s, 3 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.7,
170.5, 170.3 (3 COCH3), 145.8–128.5 (Ar-C), 91.2 (C-1), 71.2 (C-5), 64.0 (C-4),
62.8 (C-6), 44.5 (C-3), 30.1 (C-2), 21.4, 21.1, 21.0 (3 COCH3); ESI-MS: m/
z ¼ 405.4 [M þ Na]þ; Anal. Calcd. for C18H22O7S (382.43): C, 56.53; H, 5.80;
found: C, 56.38; H, 6.02.
1,4,6-Tri-O-acetyl-3-mercapto (2-methylphenyl)-2-deoxy-a-D-galactopyranose
(Table 1, entry 14): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.40–7.15 (m, 4H, Ar-H), 6.15 (dd, J ¼ 8.0,
2.2 Hz, 1H, H-4), 5.70–5.60 (m, 1H, H-1), 4.60–4.58 (m, 1H, H-3), 4.0–3.85
(m, 2H, H-6ab), 3.30–3.22 (m, 1H, H-5), 2.41 (s, 3H, CH3), 2.20, 2.12, 2.09
(3 s, 9H, 3 COCH3), 2.11–1.88 (m, 2H, H-2ea); 13C NMR (CDCl3, 50 MHz):
d 168.3, 168.2 (2 C) (3 COCH3), 140.2–126.4 (Ar-C), 92.4 (C-1), 74.3 (C-4),
65.0 (C-5), 63.3 (C-6), 46.2 (C-3), 31.9 (C-2), 21.0–20.6 (3 C, 3 COCH3), 20.4
(CH3); S-isomer: 1H NMR (CDCl3, 200 MHz): d 7.40–7.15 (m, 4H, Ar-H),
6.23 (d, J ¼ 2.2 Hz, 1H, H-4), 5.25–5.22 (m, 1H, H-1), 4.76–4.74 (m, 1H,
H-3), 4.15–4.06 (m, 2H, H-6ab), 3.52–3.61 (m, 1H, H-5), 2.43 (s, 3H, CH3),
2.09, 2.05 (2 s, 9H, 3 COCH3), 2.12–1.90 (m, 2H, H-2ea); 13C NMR (CDCl3,
50 MHz): d 169.8, 169.4 (2 C) (3 COCH3), 140.2–126.4 (Ar-C), 90.9 (C-1), 70.6
(C-4), 65.5 (C-5), 63.3 (C-6), 43.2 (C-3), 30.2 (C-2), 21.1, 20.6 (2 C) (3 COCH3),
20.3 (CH3); ESI-MS: m/z ¼ 419.5 [M þ Na]þ; Anal. Calcd. for C19H24O7S
(396.45): C, 57.56; H, 6.10; found: C, 57.38; H, 6.33.
1,4,6-Tri-O-acetyl-3-mercapto (3-methylphenyl)-2-deoxy-a-D-galactopyranose
(Table 1, entry 15): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.29–7.09 (m, 4H, Ar-H), 6.32–6.26 (m, 1H,
H-1), 5.30–5.25 (m, 1H, H-4), 5.82–5.77 (m, 1H, H-3), 4.18–4.06 (m, 2H,
H-6ab), 3.80–3.72 (m, 1H, H-5), 2.35 (s, 3H, CH3), 2.17, 2.10, 2.09 (3 s, 9H,
3 COCH3), 2.20–1.85 (m, 2H, H-2ea); 13C NMR (CDCl3, 50 MHz): d 170.0,
169.6, 168.6 (3 COCH3), 138.9–127.0 (Ar-C), 90.7 (C-1), 70.6 (C-5), 67.3 (C-4),
62.6 (C-6), 43.8 (C-3), 30.3 (C-2), 21.1, 20.8, 20.6, 20.4 (3 COCH3, CH3);
1
S-isomer: H NMR (CDCl3, 200 MHz): d 7.30–7.10 (m, 4H, Ar-H), 6.20–6.12

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
249
(m, 1H, H-1), 5.24–5.20 (m, 1H, H-4), 4.55–4.48 (m, 1H, H-3), 4.18–4.06
(m, 2H, H-6ab), 3.60–3.50 (m, 1H, H-5), 2.33 (s, 3H, CH3), 2.05, 2.03 (2 s, 9H,
3 COCH3), 2.20–1.87 (m, 2H, H-2ea); 13C NMR (CDCl3, 50 MHz): d 168.6,
168.5, 168.4 (3 COCH3), 138.9–127.0 (Ar-C), 92.7 (C-1), 74.4 (C-5), 65.2 (C-4),
62.4 (C-6), 47.6 (C-3), 31.9 (C-2), 21.1, 20.8, 20.6, 20.4 (3 COCH3, CH3); ESI-
MS: m/z ¼ 419.5 [M þ Na]þ; Anal. Calcd. for C19H24O7S (396.45): C, 57.56;
H, 6.10; found: C, 57.35; H, 6.38.
1,4,6-Tri-O-acetyl-3-mercapto (4-methylphenyl)-2-deoxy-a-D-galactopyranose
(Table 1, entry 16): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.38–7.11 (m, 4H, Ar-H), 6.10 (dd, J ¼ 8.0,
2.4 Hz, 1H, H-4), 5.75–5.65 (m, 1H, H-1), 4.52–4.50 (m, 1H, H-3), 3.98–3.80
(m, 2H, H-6ab), 3.17–3.10 (m, 1H, H-5), 2.34 (s, 3H, CH3), 2.19–2.16 (m, 1H,
H-2e), 2.11, 2.06, 2.03 (3 s, 9H, 3 COCH3), 2.05–1.90 (m, 1H, H-2a); 13C NMR
(CDCl3, 50 MHz): d 168.5 (2 C), 168.4 (3 COCH3), 138.4–127.8 (Ar-C), 92.8
(C-1), 74.5 (C-5), 65.3 (C-4), 62.4 (C-6), 48.3 (C-3), 31.9 (C-2), 21.0, 20.9 (2 C)
1
(3 COCH3), 20.7 (CH3); S-isomer: H NMR (CDCl3, 200 MHz): d 7.38–7.11
(m, 4H, Ar-H), 6.21 (d, J ¼ 2.4 Hz, 1H, H-4), 5.20–5.21 (m, 1H, H-1), 4.75–
4.74 (m, 1H, H-3), 4.13–4.09 (m, 2H, H-6ab), 3.56–3.38 (m, 1H, H-5), 2.35
(s, 3H, CH3), 2.14, 2.08, 2.02 (3 s, 9H, 3 COCH3), 2.19–2.16 (m, 1H, H-2e),
2.05–1.90 (m, 1H, H-2a); 13C NMR (CDCl3, 50 MHz): d 170.0, 169.7, 169.6 (3
COCH3), 138.4, 128.8 (Ar-C), 91.1 (C-1), 69.8 (C-5), 65.5 (C-4), 62.4 (C-6),
44.4 (C-3), 30.4 (C-2), 21.3, 21.2, 21.1 (3 COCH3), 20.8 (CH3); ESI-MS:
m/z ¼ 419.5 [M þ Na]þ; Anal. Calcd. for C19H24O7S (396.45): C, 57.56; H,
6.10; found: C, 57.37; H, 6.38.
1,4,6-Tri-O-acetyl-3-mercaptoacetyl-2-deoxy-a-D-galactopyranose (Table 1,
entry 17): R-isomer
1H NMR (CDCl3, 200 MHz): d 6.20 (d, J ¼ 2.4 Hz, 1H, H-4), 5.22–5.20
(m, 1H, H-1), 4.93–4.90 (m, 1H, H-3), 4.34–4.28 (m, 1H, H-5), 4.28–3.97
(m, 2H, H-6ab), 2.30 (s, 3H, SCOCH3), 2.11, 2.02 (2 s, 9H, 3 COCH3), 2.0–
1.80 (m, 2H, H-2ea); 13C NMR (CDCl3, 50 MHz): d 193.9 (SCOCH3), 170.5,
170.1, 170.0 (3 COCH3), 93.0 (C-1), 74.7 (C-4), 70.3 (C-5), 62.6 (C-6), 39.9
1
(C-3), 30.1 (C-2), 21.5–20.9 (4 C, SCOCH3, 3 COCH3); S-isomer: H NMR
(CDCl3, 200 MHz): d 5.81–5.77 (m, 1H, H-4), 5.17–5.14 (m, 1H, H-1), 4.64–
4.62 (m, 1H, H-3), 4.24–4.21 (m, 1H, H-5), 4.22–3.92 (m, 2H, H-6ab), 2.31
(s, 3H, SCOCH3), 2.13, 2.10, 2.06 (3 s, 9H, 3 COCH3), 2.05–1.82 (m, 2H,
H-2ea); 13C NMR (CDCl3, 50 MHz): d 193.6 (SCOCH3), 170.0, 169.2, 168.8 (3
COCH3), 98.2 (C-1), 84.3 (C-4), 70.3 (C-5), 62.4 (C-6), 39.9 (C-3), 31.3 (C-2),
21.5–20.8 (4 C, SCOCH3, 3 COCH3); ESI-MS: m/z ¼ 371.4 [M þ Na]þ; Anal.
Calcd. for C14H20O8S (348.37): C, 48.27; H, 5.79; found: C, 48.02; H, 6.0.

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1,4,6-Tri-O-acetyl-3-(ethylglycoloyl)mercapto-2,3-dideoxy-a-D-galactopyranose
(Table 1, entry 18): R-isomer
1H NMR (CDCl3, 200 MHz): d 5.93–5.90 (m, 1H, H-1), 5.28–5.27 (m, 1H,
H-4), 4.48–4.44 (m, 1H, H-5), 4.27–3.99 (m, 4H, H-6ab, OCH2CH3), 3.66–3.57
(m, 1H, H-3), 3.48–3.28 (m, 2H, SCH2COOEt), 2.17, 2.13, 2.12 (3 s, 9H,
3 COCH3), 2.05–1.91 (m, 2H, H-2ea), 1.29 (t, J ¼ 7.6 Hz, 3H, OCH2CH3); 13C
NMR (CDCl3, 50 MHz): d 169.9, 169.8, 169.6, 169.4 (3 COCH3, COOEt), 90.7
(C-1), 69.3 (C-5), 64.4 (C-4), 62.5 (C-6), 61.7 (OCH2CH3), 38.9 (C-3), 30.3 (C-2),
1
28.7 (SCH2-), 20.9–20.4 (3 C, 3 COCH3), 13.9 (-CH2CH3); S-isomer: H NMR
(CDCl3, 200 MHz): d 5.79–5.75 (m, 1H, H-1), 5.21 (brs, 1H, H-4), 4.40–4.32
(m, 1H, H-5), 4.20–3.95 (m, 4H, H-6ab, OCH2CH3), 3.50–3.43 (m, 1H, H-3),
3.33–3.15 (m, 2H, SCH2COOEt), 2.11, 2.08, 2.07 (3 s, 9H, 3 COCH3), 2.03–
1.87 (m, 2H, H-2ea), 1.30 (t, J ¼ 7.5 Hz, 3H, OCH2CH3); 13C NMR (CDCl3,
50 MHz): d 169.4, 168.5, 168.3, 168.2 (COOEt, 3 COCH3), 92.5 (C-1), 73.9 (C-5),
63.7 (C-4), 62.7 (C-6), 61.6 (OCH2CH3), 39.9 (C-3), 31.4 (C-2), 28.6 (SCH2-),
20.7–20.2 (3 C, 3 COCH3), 13.8 (-CH2CH3); ESI-MS: m/z ¼ 415.4 [M þ Na]þ;
Anal. Calcd. for C16H24O9S (392.42): C, 48.97; H, 6.16; found: C, 48.80; H, 6.38.
1,4,6-Tri-O-acetyl-3-mercapto (2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2-
deoxy-a-D-galactopyranose (Table 1, entry 19): R-isomer
1H NMR (CDCl3, 300 MHz): d 5.25 (brs, 1H, H-4), 5.15 (t, J ¼ 9.4 Hz, 1H,
H-30), 5.08 (t, J ¼ 9.4 Hz, 1H, H-20), 5.12–4.98 (m, 2H, H-1, H-40), 4.63
(d, J ¼ 9.9 Hz, 1H, H-10), 4.24–4.05 (m, 4H, H-6ab, H-6a0 b), 3.96–3.87 (m, 1H,
H-3), 3.74–3.69 (m, 1H, H-5), 3.50–3.40 (m, 1H, H-50), 2.26–1.98 (m, 2H,
H-2e0 a), 2.14, 2.13, 2.12, 2.10, 2.08, 2.06, 2.05 (7 s, 21H, 7 COCH3); 13C NMR
(CDCl3, 75 MHz): d 170.1, 169.7, 169.3, 169.1, 169.0, 168.6, 168.4 (7 COCH3),
91.0 (C-1), 82.3 (C-10, 75.9 (C-5), 73.4 (C-4), 69.9, 69.4, 68.1, 67.9, 62.3 (C-6),
1
61.7 (C-60), 37.9 (C-3), 31.5 (C-2), 20.4 (3 C), 20.3 (4 C); S-isomer: H NMR
(CDCl3, 300 MHz): d 5.21 (brs, 1H, H-4), 5.20–5.10 (m, 2H, H-20, H-30), 5.10–
4.95 (m, H-1, H-40), 4.60 (d, J ¼ 9.9 Hz, 1H, H-10), 4.30–4.10 (m, 4H, H-6ab,
H-6a0 b), 3.93–3.85 (m, 1H, H-3), 3.70–3.65 (m, 1H, H-5), 3.28–3.22 (m, 1H,
H-50), 2.20–1.88 (m, 2H, H-2e0 a), 2.15, 2.13, 2.11, 2.09, 2.08, 2.06, 2.05 (7 s,
21H, 7 COCH3); 13C NMR (CDCl3, 75 MHz): d 170.1 (2 C), 169.7, 169.2, 169.0
(2 C), 168.6 (7 COCH3), 92.5 (C-1), 82.1 (C-10), 76.1 (C-4), 74.6 (C-5), 70.4,
69.2, 67.5, 67.4, 62.0 (C-6), 61.6 (C-60), 38.8 (C-3), 30.5 (C-2), 21.0 (2 C), 20.9
(2 C), 20.8 (3 C); ESI-MS: m/z ¼ 659.6 [M þ Na]þ; Anal. Calcd. for
C26H36O16S (636.62): C, 49.05; H, 5.70; found: C, 48.82; H, 5.96.
1,4,6-Tri-O-acetyl-3-mercapto (2-pyridyl)-2-deoxy-a-D-galactopyranose
(Table 1, entry 20): R-isomer
1H NMR (CDCl3, 200 MHz): d 8.45–8.41 (m, 1H, Ar-H), 7.52–7.46 (m, 1H,
Ar-H), 7.12–7.00 (m, 2H, Ar-H), 5.98–5.82 (m, 1H, H-1), 5.42 (brs, 1H, H-4),

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
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4.70–4.60 (m, 1H, H-5), 4.42–4.35 (m, 1H, H-3), 4.20–3.95 (m, 2H, H-6ab),
2.72–2.65 (m, 1H, H-2e), 2.40–2.30 (m, 1H, H-2a), 2.17, 2.15, 2.13 (3 s, 9H,
3 COCH3); 13C NMR (CDCl3, 200 MHz): d 169.8, 169.3, 168.5 (3 COCH3),
156.3–119.4 (Ar-C), 90.9 (C-1), 69.5 (C-5), 66.5 (C-4), 62.6 (C-6), 37.6 (C-3),
1
29.2 (C-2), 20.9–20.5 (3 C, 3 COCH3); S-isomer: H NMR (CDCl3, 200 MHz):
d 8.45–8.41 (m, 1H, Ar-H), 7.52–7.46 (m, 1H, Ar-H), 7.12–7.00 (m, 2H, Ar-
H), 6.09–6.0 (m, 1H, H-1), 5.34 (brs, 1H, H-4), 4.55–4.48 (m, 1H, H-5),
4.40–4.34 (m, 1H, H-3), 4.15–3.90 (m, 2H, H-6ab), 2.88–2.77 (m, 1H, H-2e),
2.40–2.32 (m, 1H, H-2a), 2.17, 2.13, 2.11 (3 s, 9H, 3 COCH3); 13C NMR
(CDCl3, 50 MHz): d 168.5, 168.2 (2 C, 3 COCH3), 156.3–119.3 (Ar-C), 90.9 (C-
1), 70.4 (C-5), 67.2 (C-4), 62.2 (C-6), 39.7 (C-3), 30.2 (C-2), 20.6–20.4 (3 C, 3
COCH3); ESI-MS: m/z ¼ 406.4 [M þ Na]þ; Anal. Calcd. for C17H21NO7S
(383.82): C, 53.25; H, 5.52; found: C, 53.0; H, 5.74.
1,4,6-Tri-O-acetyl-3-(N-piperidinodithiocarbamoyl)-2-deoxy-a-D-
galactopyranose (Table 1, entry 21): R-isomer
1H NMR (CDCl3, 200 MHz): d 6.24–6.22 (m, 1H, H-1), 5.48 (brs, 1H, H-4),
4.81–4.74 (m, 1H, H-3), 4.40–4.29 (m, 1H, H-5), 4.24–4.17 (m, 2H, NCH2),
4.14–3.92 (m, 2H, H-6ab), 3.90–3.78 (m, 2H, NCH2), 2.30–2.21 (m, 1H,
H-2e), 2.11–2.0 (m, 1H, H-2a), 2.17, 2.12, 2.05 (3 s, 9H, 3 COCH3), 1.80–1.60
(m, 6H, 3 CH2); 13C NMR (CDCl3, 50 MHz): d 192.0 (CS), 170.2, 169.5, 169.0
(3 COCH3), 91.5 (C-1), 70.2 (C-4), 67.2 (C-5), 62.5 (C-6), 53.0 (CH2), 51.4
(CH2), 45.8 (C-3), 29.5 (C-2), 25.3 (CH2), 24.2 (2 C, 2 CH2), 20.9, 20.7, 20.6 (3
COCH3); ESI-MS: m/z ¼ 456.5 [M þ Na]þ; Anal. Calcd. for C18H27NO7S2
(433.54): C, 49.87; H, 6.28; found: C, 49.66; H, 6.5.
1,4,6-Tri-O-acetyl-3-(N-morpholinodithiocarbamoyl)-2-deoxy-a-D-
galactopyranose (Table 1, entry 22): R-isomer
1H NMR (CDCl3, 200 MHz): d 6.27–6.25 (m, 1H, H-1), 5.50 (brs, 1H, H-4),
4.85–4.75 (m, 1H, H-3), 4.62–4.52 (m, 1H, H-5), 4.45–3.96 (m, 6H, H-6ab,
2 NCH2), 3.85–3.70 (m, 4H, 2 OCH2), 2.86–2.80 (m, 1H, H-2e), 2.41–2.23
(m, 1H, H-2a), 2.20, 2.15, 2.05 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3,
50 MHz): d 193.8 (CS), 170.1, 169.6, 169.4 (3 COCH3), 91.3 (C-1), 70.0 (C-4),
66.9 (C-5), 66.0 (2 C, OCH2), 62.0 (C-6), 51.0 (2 C, NCH2), 45.8 (C-3), 29.5 (C-
2), 21.0, 20.9, 20.8 (3 COCH3); ESI-MS: m/z ¼ 458.5 [M þ Na]þ; Anal. Calcd.
for C17H25NO8S2 (435.51): C, 46.88; H, 5.79; found: C, 46.64; H, 6.0.
1,4,6-Tri-O-acetyl-3-(N,N-diethylaminodithiocarbamoyl)-2-deoxy-a-D-
galactopyranose (Table 1, entry 23): R-isomer
1H NMR (CDCl3, 200 MHz): d 6.25–6.22 (m, 1H, H-1), 5.47 (brs, 1H, H-4),
4.80–4.72 (m, 1H, H-3), 4.41–4.36 (m, 1H, H-5), 4.15–4.06 (m, 1H, H-6a), 4.04–
3.95 (m, 4H, CH2CH3), 3.72–3.62 (m, 1H, H-6b), 2.34–2.22 (m, 1H, H-2e), 2.18,
2.12, 2.05 (3 s, 9H, 3 COCH3), 2.16–2.01 (m, 1H, H-2a), 1.28–1.24 (m, 6H,

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2 COCH3); 13C NMR (CDCl3, 50 MHz): d 191.9 (CS), 170.0, 169.5, 168.9 (3
COCH3), 91.7 (C-1), 70.2 (C-4), 67.2 (C-5), 62.7 (C-6), 46.7 (2 C, 2 CH2CH3),
45.8 (C-3), 28.8 (C-2), 21.1, 20.7, 20.6 (3 COCH3), 12.4, 11.4 (2 CH2CH3); ESI-
MS: m/z ¼ 444.5 [M þ Na]þ; Anal. Calcd. for C17H27NO7S2 (421.53): C, 48.44;
H, 6.46; found: C, 48.17; H, 6.68.
1,4,6-Tri-O-acetyl-3-(1,2,3,4-tetrahydroisoquinolinodithiocarbamoyl)-2-deoxy-
a-D-galactopyranose (Table 1, entry 24): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.24–7.10 (m, 4H, Ar-H), 6.25–6.22 (m, 1H,
H-1), 5.50 (brs, 1H, H-4), 4.88–4.81 (m, 1H, H-3), 4.42–4.38 (m, 1H, H-5), 4.21–
4.07 (m, 2H, H-6a, NCH2CH2), 4.03–3.92 (m, 2H, H-6b, NCH2CH2), 3.0–2.92
(m, 2H, NCH2), 2.40–2.22 (m, 1H, H-2e), 2.16, 2.13, 2.05 (3 s, 9H, 3 COCH3),
2.11–2.03 (m, 1H, H-2a); 13C NMR (CDCl3, 50 MHz): d 193.0 (CS), 170.1,
169.5, 168.9 (3 COCH3), 134.9–126.0 (Ar-C), 91.5 (C-1), 70.2 (C-4), 67.0 (C-5),
62.4 (C-6), 53.8 (NCH2CH2), 47.9 (NCH2CH2), 45.5 (C-3), 29.6 (C-2), 28.9
(NCH2), 21.0, 20.8, 20.7 (3 COCH3); ESI-MS: m/z ¼ 504.6 [M þ Na]þ; Anal.
Calcd. for C22H27NO7S2 (481.58): C, 54.87; H, 5.65; found: C, 54.65; H, 6.90.
4,6-Di-O-acetyl-3-mercaptophenyl-2-deoxy-D-glucono-1,5-lactone (Table 1,
entry 25): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.50–7.31 (m, 5H, Ar-H), 5.21–5.10 (m, 1H,
H-4), 4.50–4.35 (m, 1H, H-5), 4.30–4.20 (m, 2H, H-6ab), 3.58–3.42 (m, 1H,
H-3), 3.0–2.75 (m, 2H, H-2ea), 2.05, 2.03 (2 s, 6H, 2 COCH3); 13C NMR
(CDCl3, 50 MHz): d 170.1, 169.3, 166.6 (2 COCH3, C-1), 134.1–127.9 (Ar-C),
77.9 (C-5), 68.2 (C-4), 61.6 (C-6), 42.8 (C-3), 33.5 (C-2), 20.7, 20.5 (2 COCH3);
1
R-isomer: H NMR (CDCl3, 200 MHz): d 7.50–7.31 (m, 5H, Ar-H), 5.29–5.20
(m, 1H, H-4), 4.90–4.79 (m, 1H, H-5), 4.28–4.21 (m, 2H, H-6ab), 3.86–3.75
(m, 1H, H-3), 3.0–2.85 (m, 1H, H-2e), 2.62–2.50 (m, 1H, H-2a), 2.04, 2.03
(2 s, 6H, 2 COCH3); 13C NMR (CDCl3, 50 MHz): d 169.8, 169.6, 167.2 (2
COCH3, C-1), 134.2–127.9 (Ar-C), 77.2 (C-5), 67.2 (C-4), 62.8 (C-6), 42.9
(C-3), 34.5 (C-2), 20.6, 20.5 (2 COCH3); ESI-MS: m/z ¼ 361.4 [M þ Na]þ;
Anal. Calcd. for C16H18O6S (338.38): C, 56.79; H, 5.36; found: C, 56.55; H, 6.58.
4,6-Di-O-acetyl-3-mercapto (2-methylphenyl)-2-deoxy-D-glucono-1,5-lactone
(Table 1, entry 26): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.40–7.10 (m, 4H, Ar-H), 5.15–5.06 (m, 1H,
H-4), 4.78–4.68 (m, 1H, H-5), 4.28–4.05 (m, 2H, H-6ab), 3.72–3.64 (m, 1H,
H-3), 2.92–2.70 (m, 2H, H-2ea), 2.36 (s, 3H, CH3), 1.99, 1.97 (2 s, 6H,
2 COCH3); 13C NMR (CDCl3, 50 MHz): d 169.8, 169.6, 166.8 (2 COCH3, C-1),
141.0–126.8 (Ar-C), 77.0 (C-5), 67.4 (C-4), 62.8 (C-6), 42.2 (C-3), 33.7 (C-2),
1
20.9, 20.6, 20.5 (2 COCH3, CH3); R-isomer: H NMR (CDCl3, 200 MHz): d
7.40–7.10 (m, 4H, Ar-H), 5.22–5.12 (m, 1H, H-4), 4.40–4.28 (m, 1H, H-5),
4.27–4.08 (m, 2H, H-6ab), 4.52–4.40 (m, 1H, H-3), 2.99–2.85 (m, 1H, H-2e),

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
253
2.60–2.40 (dd, J ¼ 17.4, 9.2 Hz, 1H, H-2a), 2.37 (s, 3H, CH3), 2.02, 1.93 (2 s, 6H,
2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.1, 169.2, 166.9 (2 COCH3, C-1),
141.1–126.8 (Ar-C), 77.8 (C-5), 68.7 (C-4), 62.5 (C-6), 43.9 (C-3), 34.4 (C-2),
20.8, 20.6, 20.5 (2COCH3, CH3); ESI-MS: m/z ¼ 375.4 [M þ Na]þ; Anal.
Calcd. for C17H20O6S (352.4): C, 57.94; H, 5.72; found: C, 57.70; H, 6.0.
4,6-Di-O-acetyl-3-mercapto (3-methylphenyl)-2-deoxy-D-glucono-1,5-lactone
(Table 1, entry 27): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.26–7.11 (m, 4H, Ar-H), 5.24–5.20 (m, 1H,
H-4), 5.82–4.72 (m, 1H, H-5), 4.30–4.26 (m, 2H, H-6ab), 4.88–4.76 (m, 1H,
H-3), 3.02–2.76 (m, 2H, H-2ea), 2.35 (s, 3H, CH3), 2.04, 2.03 (2 s, 6H,
2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.3, 169.8, 167.3 (2 COCH3, C-1),
139.2–126.4 (Ar-C), 81.5 (C-5), 70.8 (C-4), 61.7 (C-6), 42.9 (C-3), 35.5 (C-2),
1
21.3, 20.8, 20.6 (2 COCH3, CH3); R-isomer: H NMR (CDCl3, 200 MHz): d
7.28–7.11 (m, 4H, Ar-H), 5.18 (t, J ¼ 8.4 Hz, 1H, H-4), 4.40–4.28 (m, 1H,
H-5), 4.30–4.25 (m, 2H, H-6ab), 3.58–3.42 (m, 1H, H-3), 3.06–2.82 (m, 1H,
H-2e), 2.60–2.20 (dd, J ¼ 17.6, 9.5 Hz, 1H, H-2a), 2.35 (s, 3H, CH3), 2.04, 2.03
(2 s, 6H, 2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.4, 170.0, 166.9 (2
COCH3, C-1), 139.2–126.8 (Ar-C), 81.4 (C-5), 67.9 (C-4), 62.1 (C-6), 41.6 (C-
3), 34.7 (C-2), 21.3, 20.9, 20.7 (2 COCH3, CH3); ESI-MS: m/z ¼ 375.4
[M þ Na]þ; Anal. Calcd. for C17H20O6S (352.4): C, 57.94; H, 5.72; found: C,
57.72; H, 5.95.
4,6-Di-O-acetyl-3-mercapto (4-methylphenyl)-2-deoxy-D-glucono-1,5-lactone
(Table 1, entry 28): S-isomer
1H NMR (CDCl3, 200 MHz): d 7.38–7.10 (m, 4H, Ar-H), 5.11 (t, J ¼ 8.0 Hz,
1H, H-4), 4.55–4.40 (m, 1H, H-5), 4.30–4.15 (m, 2H, H-6ab), 3.50–3.32 (m, 1H,
H-3), 3.0–2.77 (m, 1H, H-1e), 2.60–2.40 (dd, J ¼ 17.5, 9.4 Hz, 1H, H-2a), 2.35
(s, 3H, CH3), 2.08, 2.06 (2 s, 6H, 2 COCH3); 13C NMR (CDCl3, 50 MHz): d
169.8, 169.6, 167.3 (2 COCH3, C-1), 139.2–126.6 (Ar-C), 77.8 (C-5), 67.9 (C-
4), 62.6 (C-6), 44.2 (C-3), 34.5 (C-2), 21.2, 20.7, 20.5 (2 COCH3, CH3);
1
R-isomer: H NMR (CDCl3, 200 MHz): d 7.38–7.12 (m, 4H, Ar-H), 5.22–5.18
(m, 1H, H-4), 4.82–4.72 (m, 1H, H-5), 4.28–4.10 (m, 2H, H-6ab), 3.78–3.65
(m, 1H, H-3), 3.0–2.70 (m, 2H, H-2ea), 2.35 (s, 3H, CH3), 2.06, 2.03 (2 s, 6H,
2 COCH3); 13C NMR (CDCl3, 50 MHz): d 169.9, 169.8, 166.7 (2 COCH3, C-1),
139.2–126.6 (Ar-C), 77.3 (C-5), 67.2 (C-4), 62.9 (C-6), 43.1 (C-3), 33.4 (C-2),
20.8, 20.6, 20.5 (2 COCH3, CH3); ESI-MS: m/z ¼ 375.4 [M þ Na]þ; Anal.
Calcd. for C17H20O6S (352.4): C, 57.94; H, 5.72; found: C, 57.70; H, 6.0.
4,6-Di-O-acetyl-3-mercaptoacetyl-2-deoxy-D-glucono-1,5-lactone (Table 1,
entry 29): S-isomer
1H NMR (CDCl3, 200 MHz): d 5.50–5.40 (m, 1H, H-4), 5.30–5.20 (m, 1H,
H-5), 4.40–4.30 (m, 1H, H-3), 4.25–4.10 (m, 2H, H-6ab), 2.80–2.40

P. K. Mandal et al.
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(m, 2H, H-2ea), 2.32 (s, 3H, CH3), 2.11, 2.08 (2 s, 6H, 2 COCH3); 13C NMR
(CDCl3, 50 MHz): d 171.2, 170.9, 170.6, 167.2 (3 COCH3, C-1), 71.2 (C-5),
70.0 (C-4), 62.2 (C-6), 40.9 (C-3), 35.4 (C-2), 21.3, 21.0, 20.9 (3 COCH3);
1
R-isomer: H NMR (CDCl3, 200 MHz): d 5.32–5.28 (m, 1H, H-4), 5.25–5.20
(m, 1H, H-5), 4.30–4.28 (m, 1H, H-3), 4.26–4.10 (m, 2H, H-6ab), 2.78–2.35
(m, 2H, H-2a), 2.35 (s, 3H, CH3), 2.07, 2.05 (2 s, 6H, 2 COCH3); 13C NMR
(CDCl3, 50 MHz): d 171.4, 170.2, 170.0, 166.9 (3 COCH3, C-1), 70.8 (C-5),
69.8 (C-4), 62.2 (C-6), 40.2 (C-3), 35.2 (C-2), 21.3, 21.2, 21.0 (3 COCH3);
ESI-MS: m/z ¼ 327.3 [M þ Na]þ; Anal. Calcd. for C12H16O7S (304.32): C,
47.36; H, 5.30; found: C, 47.12; H, 5.52.
4,6-Di-O-acetyl-3-mercapto (2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2-
deoxy-D-glucono-1,5-lactone (Table 1, entry 30): S-isomer
1H NMR (CDCl3, 300 MHz): d 5.30–5.26 (m, 1H, H-4), 5.22 (t, J ¼ 9.3 Hz,
1H, H-30), 5.07–5.01 (2 t, J ¼ 9.4, 9.4 Hz, 2H, H-20, H-40), 4.68–2.62 (m, 1H,
H-5), 4.52 (d, J ¼ 9.8 Hz, 1H, H-10), 4.46–4.41 (m, 1H, H-6a0 ), 4.30–4.20
(m, 2H, H-6ab), 4.10–4.04 (m, 1H, H-6b0 ), 3.84–3.70 (m, 2H, H-3, H-50), 2.96–
2.87 (m, 1H, H-1e), 2.78–2.62 (m, 1H, H-1a), 2.18, 2.13, 2.09, 2.06, 2.02, 2.00
(6 s, 18H, 6 COCH3); 13C NMR (CDCl3, 75 MHz): d 170.2, 170.1, 169.9, 169.5,
169.2, 169.0 (6 COCH3), 165.2 (C-1), 82.0 (C-10), 77.8, 74.0, 73.5, 68.9, 68.8,
67.9, 62.5 (C-6), 61.7 (C-60), 37.2 (C-3), 31.6 (C-2), 20.8 (2 C), 20.6 (2 C), 20.5
(2 C); ESI-MS: m/z ¼ 615.5 [M þ Na]þ; Anal. Calcd. for C24H32O15S (592.57):
C, 48.65; H, 5.44; found: C, 48.46; H, 5.68.
4,6-Di-O-acetyl-3-mercaptophenyl-2-deoxy-D-galactono-1,5-lactone (Table 1,
entry 31): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.50–7.34 (m, 5H, Ar-H), 5.12–5.06 (m, 2H,
H-3, H-4), 4.22–4.19 (m, 2H, H-6), 3.77–3.70 (m, 1H, H-5), 3.06 (dd, J ¼ 18.1,
6.7 Hz, 1H, H-2e), 2.66 (dd, J ¼ 18.1, 3.7 Hz, 1H, H-2a), 2.09, 2.05 (2 s, 6H,
2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.0, 169.2, 166.7 (2 COCH3, C-1),
133.6–127.7 (Ar-C), 74.2 (C-5), 67.2 (C-4), 62.0 (C-6), 42.1 (C-3), 31.8 (C-2),
20.9, 20.6 (2 COCH3); ESI-MS: m/z ¼ 361.4 [M þ Na]þ; Anal. Calcd. for
C16H18O6S (338.38): C, 56.79; H, 5.36; found: C, 56.57; H, 6.53.
4,6-Di-O-acetyl-3-mercapto (2-methylphenyl)-2-deoxy-D-galactono-1,5-lactone
(Table 1, entry 32): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.47–7.19 (m, 4H, Ar-H), 5.14–5.07 (m, 1H,
H-3), 5.06–5.03 (m, 1H, H-4), 4.23–4.19 (m, 2H, H-6), 3.72–3.68 (m, 1H, H-5),
3.05 (dd, J ¼ 18.0, 6.7 Hz, 1H, H-2e), 2.60 (dd, J ¼ 18.1, 3.7 Hz, 1H, H-2a), 2.45
(s, 3H, CH3), 2.09, 2.05 (2 s, 6H, 2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.0,
169.2, 166.7 (2 COCH3, C-1), 140.4–127.0 (Ar-C), 74.3 (C-5), 67.1 (C-4), 61.9 (C-
6), 41.3 (C-3), 31.8 (C-2), 20.7, 20.6, 20.5 (2 COCH3, CH3); ESI-MS: m/z ¼ 375.4

Synthesis of 3-Thio-2-deoxysugar Derivatives in Water
255
[M þ Na]þ; Anal. Calcd. for C17H20O6S (352.4): C, 57.94; H, 5.72; found: C,
57.70; H, 5.96.
4,6-Di-O-acetyl-3-mercapto (3-methylphenyl)-2-deoxy-D-galactono-1,5-lactone
(Table 1, entry 33): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.28–7.13 (m, 4H, Ar-H), 5.12–5.05 (m, 2H,
H-3, H-4), 4.22–4.18 (m, 2H, H-6), 3.74–3.70 (m, 1H, H-5), 3.0 (dd, J ¼ 18.1,
6.7 Hz, 1H, H-2e), 2.60 (dd, J ¼ 18.1, 3.7 Hz, 1H, H-2a), 2.36 (s, 3H, CH3),
2.10, 2.05 (2 s, 6H, 2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.0, 169.2,
166.8 (2 COCH3, C-1), 139.4–127.9 (Ar-C), 74.2 (C-5), 67.2 (C-4), 62.0 (C-6),
42.0 (C-3), 31.8 (C-2), 21.3, 20.6, 20.5 (2 COCH3, CH3); ESI-MS: m/z ¼ 375.4
[M þ Na]þ; Anal. Calcd. for C17H20O6S (352.4): C, 57.94; H, 5.72; found: C,
57.75; H, 6.0.
4,6-Di-O-acetyl-3-mercapto (4-methylphenyl)-2-deoxy-D-galactono-1,5-lactone
(Table 1, entry 34): R-isomer
1H NMR (CDCl3, 200 MHz): d 7.38–7.14 (m, 4H, Ar-H), 5.07–5.04 (m, 2H,
H-3, H-4), 4.21–4.18 (m, 2H, H-6), 3.67–3.64 (m, 1H, H-5), 3.0 (dd, J ¼ 18.1,
6.7 Hz, 1H, H-2e), 2.60 (dd, J ¼ 18.1, 3.7 Hz, 1H, H-2a), 2.36 (s, 3H, CH3),
2.09, 2.05 (2 s, 6H, 2 COCH3); 13C NMR (CDCl3, 50 MHz): d 170.5, 168.9,
166.7 (2 COCH3, C-1), 138.9–127.2 (Ar-C), 74.2 (C-5), 68.2 (C-4), 62.0 (C-6),
42.5 (C-3), 31.8 (C-2), 21.1, 21.1, 20.6 (2COCH3, CH3); ESI-MS: m/z ¼ 375.4
[M þ Na]þ; Anal. Calcd. for C17H20O6S (352.4): C, 57.94; H, 5.72; found: C,
57.72; H, 5.98.
4,6-Di-O-acetyl-3-mercapto (2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-2-
deoxy-D-galactono-1,5-lactone (Table 1, entry 35): R-isomer
1H NMR (CDCl3, 300 MHz): d 5.29 (brs, 1H, H-4), 5.24–5.0 (m, 3H, H-20,
H-30, H-40), 4.65 (d, J ¼ 9.7 Hz, 1H, H-10), 4.28–4.06 (m, 4H, H-6ab, H-6a0 b),
3.74–3.65 (m, 2H, H-5, H-50), 3.0 (dd, J ¼ 18.1, 6.6 Hz, 1H, H-2e), 2.40 (dd,
J ¼ 18.1, 3.7 Hz, 1H, H-2a), 2.16, 2.09, 2.07, 2.03, 2.02 (5 s, 18H, 6 COCH3);
13C NMR (CDCl3, 75 MHz): d 170.3, 170.1, 169.7, 169.4, 169.2, 169.0 (6
COCH3), 166.4 (C-1), 82.3 (C-10), 78.2, 76.2, 73.4, 69.2, 68.0, 67.8, 62.7 (C-6),
61.9 (C-60), 36.2 (C-3), 32.6 (C-2), 20.6 (2 C), 20.5 (2 C), 20.4 (2 C); ESI-MS:
m/z ¼ 615.5 [M þ Na]þ; Anal. Calcd. for C24H32O15S (592.57): C, 48.65; H,
5.44; found: C, 48.48; H, 5.70.
ACKNOWLEDGMENTS
Instrumentation facilities from SAIF, CDRI, are gratefully acknowledged. P.K.M.
thanks CSIR, New Delhi, for providing a Junior Research Fellowship. This work
was partly funded by Ramanna fellowship, DST, New Delhi (AKM).

P. K. Mandal et al.
256
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