Reduction of 2-arylthio -β C-D-glucopyranosides with different functional groups in the lateral chain

Article abstract of DOI:10.1080/00397911.2010.481738

2-Arylthio -β C-D-glucopyranosides with a carbonyl or methoxy group in the lateral chain (1 and 2) can be converted to the corresponding 2-deoxy -β C-D-glucopyranosides (1a and 2a) using Raney Ni. Reduction of 2-arylthio -β C-D-glucopyranosides bearing an

Full text of DOI:10.1080/00397911.2010.481738

Synthetic Communications1, 41: 1192–1199, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.481738
REDUCTION OF 2-ARYLTHIO-b-C-
D-GLUCOPYRANOSIDES WITH DIFFERENT
FUNCTIONAL GROUPS IN THE LATERAL CHAIN
Mingming Han and Irina P. Smoliakova
Chemistry Department, University of North Dakota, Grand Forks,
North Dakota, USA
GRAPHICAL ABSTRACT
Abstract 2-Arylthio-b-C-D-glucopyranosides with a carbonyl or methoxy group in the
lateral chain (1 and 2) can be converted to the corresponding 2-deoxy-b-C-
D-glucopyranosides (1a and 2a) using Raney Ni. Reduction of 2-arylthio-b-C-
=
D-glucopyranosides bearing an ester, methoxy, CꢀN, or C C moiety in the side chain
(3–6) using n-Bu3SnH in the presence of azobisisobutyronitrile (AIBN) provided the cor-
responding 2-deoxy-b-C-D-glucopyranosides (3a–6a) without reducing additional func-
tional groups. The application of n-Bu3SnH and AIBN in reaction with 2-arylthio-b-C-
D-glucopyranoside (7) containing a Me3Si group bonded to the carbonyl fragment (7)
=
resulted in the reduction of both the 2-ArS and C O groups.
Keywords 2-Arylthio-b-C-D-glucopyranosides; 2-deoxy-b-C-D-glucopyranosides; b-C-
D-glucopyranosides; Raney Ni; tributyltin hydride
INTRODUCTION
Stereoselective synthesis of C-b-D-glycosides, including their 2-deoxy deriva-
tives, is of great interest because compounds of this class are found in nature and
some of them exhibit physiological activity of various types.[1] C-Glycosides can also
serve as nonhydrolizable enzyme inhibitors,[2] stable carbohydrate mimetics for the
Received August 3, 2009.
Address correspondence to Irina P. Smoliakova, Chemistry Department, University of North
Dakota, 151 Cornell St., Mail Stop 9024, Grand Forks, ND 58202-9024, USA. E-mail: ismoliakova@
chem.und.edu
1192

2-ARYLTHIO-b-C-D-GLUCOPYRANOSIDES
1193
Scheme 1. Two-step synthesis of 2-deoxy-b-C-D-glucopyranosides from D-glucals.
study of carbohydrate recognition in biological systems,[3] and chiral precursors for
the synthesis of other important compounds.[4]
Previously, we have reported a general method for preparation of 2-arylthio-C-
b-D-glucopyranosides from tri-O-benzyl-D-glucal.[5] In the proposed one-pot proto-
col, (i) tri-O-benzyl-D-glucal reacts with ArSCl, (ii) using a Lewis acid, the formed
ArSCl adducts of the glucal are converted to the corresponding episulfonium ions,
and (iii) the S-stabilized three-membered intermediates react with C-nucleophiles
[e.g., vinyl ethers, trimethyl cyanide (TMSCN), allyltrimethylsilane, trimethylsilyl
enol ethers, and trimethylsilyl ketene acetals] to yield 2-arylthio-C-b-glucopyrano-
sides with high stereoselectivity (b-gluco=a-manno up to 95:5, Scheme 1, step 1).
Here we report two general procedures for the removal of the arylthio group from
2-arylthio-C-b-glucosides (1–7) having various functional groups in the lateral chain
(Scheme 1, step 2).
RESULTS
2-Arylthio-C-b-glycosides 1–7 (Table 1) were synthesized by the previously
described method from tri-O-benzyl-D-glucal, ArSCl, and one of the following
C-nucleophiles: 1-(trimethylsiloxy)cyclohexene,[6] methyl vinyl ether,[7] 1-methoxy-2-
methyl-1-(trimethylsiloxy)propene,[6] 1-methoxy-2-methylpropene,[7] trimethylsilyl
cyanide,[6] allyltrimethylsilane,[6] and 1-(trimethylsilyl)-1-(trimethylsiloxy)ethylene.[7]
To obtain the desired 2-deoxy-b-C-glycosides, the 2-p-TolS group in compounds 1–7
had to be removed. In this study, two distinct methods were used.
Raney Ni is one of the most common reducing agents for ArS-substituted
compounds.[8] In particular, this method was successfully used for desulfurization
of S-containing O-glycosides.[9,10] In our study, reduction of the 2-p-TolS-substituted
C-glycoside
1 by Raney Ni at room temperature yielded 2-deoxy-b-C-
=
D-glucopyranoside 1a (Table 1). As expected, the ketone C O moiety in the lateral
chain remained intact.[11] A similar result was obtained for compound 2. However,
we found that many factors—reactivity of Raney Ni, reaction time, temperature,
and concentration of C-glucosides—have effects on the reproduction of the results.
For example, higher temperature and longer reaction time led to the partial removal
of benzyl groups. This prompted us to test n-Bu3SnH for reduction of 2-ArS-
substituted C-glycosides.
We found that the desulfurization of C-glycosides 3–6 by Bu3SnH readily
occurred in toluene at 105 ꢁC. The reactions required the use of azobisisobutyroni-
trile (AIBN) as a radical initiator. Regardless the functional group—an ester, meth-
=
oxy, CꢀN, or C C group—present in the lateral chain of glucosides 3–6, only the

1194
M. HAN AND I. P. SMOLIAKOVA
Table 1. Reduction of 2-p-tolylthio-b-C-glucopyranosides
Reducing
agent
Yield
(%)
Entry
2-p-TolS-b-C-glucopyranoside
Product
1
Raney Ni
51
84
n
2
Raney Ni
1
3
4
n-Bu3SnH
n-Bu3SnH
92
85
5
6
n-Bu3SnH
n-Bu3SnH
91
90
7
n-Bu3SnH
35
ArS group was removed, providing the corresponding 2-deoxy derivatives in good
yield (Table 1). As expected,[12] the use of Bu3SnH=AIBN in the reaction of C-glyco-
side 7 with the lateral chain containing a Me3Si group bonded to the carbonyl moiety
and provided 2-deoxy compound 7a with a hydroxyl group.
The elemental composition of 2-deoxy-b-C-glycosides 1a–7a was confirmed by
high-resolution mass spectrographic (HRMS) data. The structures of synthesized

2-ARYLTHIO-b-C-D-GLUCOPYRANOSIDES
1195
1
compounds were determined using H, 13C, correlation spectroscopy (COSY), and
distortion less enhancement by polarization transfer (DEPT) NMR spectra.
In summary, we described the desulfurization step of the two-pot protocol for
the stereoselective synthesis of b-C-D-glucopyranosides with additional functional
groups in the lateral chain from commercially available tri-O-benzyl-D-glucal.
EXPERIMENTAL
Instrumentation and Materials
1H and 13C NMR spectra (300 MHz and 75 MHz, respectively) were recorded
on a 300-MHz Varian NMR spectrometer using CDCl3 as a solvent and Me4Si as a
standard unless stated otherwise. Coupling constants, J, are given in hertz. Infrared
(IR) spectra were recorded on an ATI Mattson Genesis Series Fourier transform
(FT)-IR instrument. Optical rotations were measured on a Rudolph Autopol III
automatic polarimeter. HRMS were recorded at the University of California, River-
side, using VG-ZAB (FAB) or VG-7070 (CI=NH3) mass spectrometers.
All reactions were carried out in dry nitrogen using oven-dried or flame-dried
glassware and freshly distilled and dried solvents. Preparative thin-layer chromato-
graphy (TLC) was carried out by using glass plates, 200 ꢂ 250 mm, with an unfixed
layer of Sigma-Aldrich or Natland silica gel 60 (230–400 mesh). The purity of the
1
1
synthesized compounds was confirmed by analytical TLC, H and 13Cf Hg NMR
spectra.
General Procedure for the Synthesis of 2-Arylthio-b-C-
D-glucopyranosides 1–6[6,7]
A solution of 0.25 mmol of p-TolSCl in 0.3 mL of CH2Cl2 was added dropwise
to a solution of 0.25 mmol of tri-O-benzyl-D-glucal in 10 mL of CH2Cl2 at room tem-
perature. The color of the reaction mixture changed from yellow to colorless. After
10 min, the mixture was cooled to ꢃ78 ꢁC, and a solution of 0.3 mmol of SnCl4 in
0.3 mL CH2Cl2 was added, followed by 0.3 mmol of the corresponding C-Nu. The
mixture was stirred for 1 h at ꢃ78 ꢁC, quenched with a saturated solution of
NaHCO3 (in the case of compound 2, the reaction mixture was first treated with a
solution of n-Bu4NBH4 in CH2Cl2), extracted with ether, and dried over Na2SO4.
Preparative TLC (diethyl ether–hexane, 1:4) of the crude material after solvent
removal in vacuum afforded a pure C-glycoside.
Reduction method A. A solution of 0.100 mmol of 2-arylthio-C-b-
D-glucopyranoside in 2 mL abs. THF was treated with a freshly made[13] W-2 Raney
nickel (0.630 g). The reaction mixture was stirred at room temperature for 4–10 h,
and its composition was monitored by TLC every hour. The nickel was removed
by filtration. After solvent removal in vacuum, preparative TLC (diethyl ether–
hexane, 1:4) of the crude product provided a pure C-glycoside.
Reduction method B. To a solution of 0.100 mmol of 2-arylthio-b-C-
D-glucopyranoside in 1 mL of abs. toluene, 0.120 mmol Bu3SnH and 10 mg AIBN
were added. The reaction mixture was stirred at 105 ꢁC for 12 h; 10 mg AIBN were

1196
M. HAN AND I. P. SMOLIAKOVA
added every 4 h. After cooling the mixture to rt, the solvent was removed in vacuum.
Preparative TLC (diethyl ether–hexane, 1:4) of the crude product afforded a pure
C-glycoside.
3,4,6-(Tri-O-benzyl)-2-deoxy-1-(1’-oxocyclohexanyl)-b-D-
glucopyranoside (1a)
The compound was synthesized from 1 (0.100 mmol, 63.7 mg) by method A in
20
a yield of 51% (26.2 mg). Rf 0.38 (diethyl ether–hexane, 1:1); ½aꢄD þ 8.35 (c 0.470,
1
CHCl3); IR (film): 1706 cmꢃ1 (C O); H NMR (500 MHz, d, ppm): 1.26 [q, J2a,2b
=
ꢅ J1.2a ꢅ J3,2a ꢅ 11.5, 1H, H(2a)], 1.48–1.75, 1.90, 2.05, 2.28–2.48 (m, 9H, 9H of
cyclohexanone), 2.44 [m, 1H, H(2b)], 3.36 [dt, J4,5 ¼ 9.5, J5,6a ¼ J5,6b ¼ 3.0, 1H,
0
(5)], 3.50 [t, J3,4 ¼ J4,5 ¼ 9.5, 1H, H(4)], 3.61 [ddd, J1,2b ¼ 11.0, J1,1 ¼ 7.5,
J1,2a ¼ 1.5, 1H, H(1)], 3.70 [m, 2H, H(6ab)], 3.73 [m, 1H, H(3)], 4.54 and 4.61 (two
d, JAB ¼ 12.5, 2H, CH2Ph), 4.55 and 4.91 (two d, JAB ¼ 10.5, 2H, CH2Ph), 4.60
and 4.70 (two d, JAB ¼ 11.5, 2H, CH2Ph), 7.30 (m, 15H, H arom); 13C NMR (d,
ppm): 24.65 (CH2), 28.19 (CH2), 30.29 (CH2), 35.45 (CH2), 42.81 (CH2CO), 55.46
(CHCO), 69.45, 71.29, 73.33 and 73.70 (4 groups OCH2), 74.90, 78.36, 79.00 and
81.07 (4 groups OCH), 127.47, 127.51, 127.68, 127.93, 128.27, 128.34, 138.43 and
þ
=
138.58 (C arom). 211.66 (C O). HRMR calcd for C33H38O5 (M ) m=e 514.2720;
found m=e 514.2735.
1-(3,4,6-Tri-O-benzyl-2-deoxy-b-D-glucopyranosyl)-
2-methoxyethane (2a)
The compound was synthesized from 2 (0.100 mmol, 59.9 mg) by method A in
22
a yield of 84% (40.0 mg). Rf 0.30 (diethyl ether–hexane, 1:1); ½aꢄD þ 12.1 (c 0.240,
1
CHCl3); H NMR (500 MHz, d, ppm): 1.45 [q, J2a,2b ꢅ J1.2aꢅ J3,2a ꢅ 11.0, 1H,
H(2a)], 1.76 [m, 1H, H(1a’)], 1.90 [m, 1H, H(1b’)], 2.17 [br, dd, J2a,2b ¼ 11.0,
J2b,3 ¼ 5.0, 1H, H(2b)], 3.35 (s, 3H, OCH3), 3.52 [m, 4H, H(1), H(3), H(7ab)], 3.66
[dd, J4,5 ¼ 6.4, J3,4 ¼ 8.4, 1H, H(4)], 3.72 [m, 2H, H(6ab)], 4.57 and 4.92 (two d,
JAB ¼ 10.7, 2H, CH2Ph), 4.58 and 4.65 (two d, JAB ¼ 12.2, 2H, CH2Ph), 4.66 and
4.72 (two d, JAB ¼ 11.6, 2H, CH2Ph), 7.30 (m, 15 H, H arom); 13C NMR (d,
ppm): 35.67 and 37.06 (2 groups CH2), 58.63 (OCH3), 60.29, 69.53, 71.39, 72.61
and 73.58 (5 groups OCH2), 74.95, 78.56, 78.89 and 81.12 (4 groups OCH),
127.48, 127.55, 127.63, 127.56, 127.96, 128.29 and 128.37 (C arom). HRMS calcd.
for C30H36O5 (Mþ) m=e 476.2563; found m=e 476.2631.
Methyl 2-(3,4,6-Tri-O-benzyl-2-deoxy-b-D-glucopyranosyl)-
2-methylpropionate (3a)
The compound was obtained from glycoside 3 (0.100 mmol, 64.1 mg) by
22
method B in 92% yield (47.7 mg). Rf 0.34 (diethyl ether–hexane, 1:2); ½aꢄD þ 10.9
1
(c 0.880, CHCl3); IR (CHCl3 soln.): 1727 cmꢃ1 (C O); H NMR (d, ppm): 1.18
=
and 1.26 [two s, 6H, C(CH3)2], 1.48 [q, J1,2a ¼ J2a,3 ¼ 11.2, J2a,2b ¼ 12.3, 1H,
H(2a)], 2.40 [dd, J2a,2b ¼ 12.3, J2b,3 ¼ 4.9, 1H, H(2b)], 3.43 [ddd, J4,5 ¼ 9.3,
J5,6a ¼ 2.9, J5,6b ¼ 5.6, 1H, H(5)], 3.51 [t, J3,4 ¼ J4,5 ¼ 9.3, 1H, H(4)], 3.62 [d,

2-ARYLTHIO-b-C-D-GLUCOPYRANOSIDES
1197
J1,2a ¼ 11.2, 1H, H(1)], 3.68 (s, 3H, OCH3), 3.75 [m, 3H, H(6ab), H(3)], 4.57 and 4.63
(two d, JAB ¼ 12.3, 2H, CH2Ph), 4.65 and 4.92 (two d, JAB ¼ 10.8, 2H, CH2Ph), 4.68
and 4.72 (two d, JAB ¼ 11.5, 2H, CH2Ph), 7.31 (m, 15H, H arom); 13C NMR (d,
ppm): 21.00 and 21.30 [C(CH3)2], 31.42 (CH2), 46.41 [C(CH3)2], 52.11 (OCH3),
69.56, 71.86, 73.39 and 75.20 (4 groups OCH2), 78.88, 79.72, 79.79 and 81.52 (4
groups OCH), 127.54, 127.68, 127.74, 127.82, 128.19, 128.46, 128.53, 128.59,
þ
=
138.74 and 138.92 (C arom). 177.05 (C O). HRMS calcd. for C32H38O6(M ) m=e
518.2669; found for (M þ 1)þ m=e 519.2751.
1-Methoxy-2-methyl-2-(3,4,6-tri-O-benzyl-2-deoxy-b-D-
glucopyranosyl)propane (4a)
The compound was obtained from glycoside 4 (0.100 mmol, 62.7 mg) by
20
method B in 85% yield (42.9 mg). Rf 0.45 (diethyl ether–hexane, 1:2); ½aꢄD þ 8.4 (c
1
0.50, CHCl3); H NMR (d, ppm): 0.90 and 0.94 [two s, 6H, C(CH3)2], 1.45 [q,
J1,2a ¼ 11.7, J2a,2b ¼ 12.1, J2a,3 ¼ 13.4, 1H, H(2a)], 2.07 [ddd, J2a,2b ¼ 12.1,
J2b,3 ¼ 5.0, J1,2b ¼ 1.4, 1H, H(2b)], 3.14 and 3.26 (two d, J7a,7b ¼ 8.9, 2H, CH2OCH3),
3.25 [dd, J1,2b ¼ 1.4, J1,2a ¼ 11.7, H(1)], 3.30 (s, 3H, OCH3), 3.36 [dt, J4,5 ¼ 9.5,
J5,6a ¼ J5,6b ¼ 6.4, 1H, H(5)], 3.45 [t, J3,4 ¼ J4,5 ¼ 9.5, 1H, H(4)], 3.65 [ddd,
J3,2a ¼ 13.4, J3,4 ¼ 9.5, J3,2b ¼ 5.0, 1H, H(3)], 3.75 [m, 2H, H(6a,b)], 4.57 and 4.72
(two d, JAB ¼ 11.6, 2H, CH2Ph), 4.58 and 4.65 (two d, JAB ¼ 12.2, 2H, CH2Ph),
4.63 and 4.91 (two d, JAB ¼ 10.9, 2H, CH2Ph), 7.30 (m, 15H, H arom); 13C NMR
(d, ppm): 20.70 and 21.67 [C(CH3)2], 31.24 (CH2), 38.38 [C(CH3)2], 59.55 (OCH3),
70.99, 71.82, 73.46, 75.14 and 79.47 (5 groups OCH2), 79.07, 79.20, 79.83 and
82.04 (4 groups OCH), 127.56, 127.68, 127.77, 127.86, 128.21, 128.48, 128.54,
128.69, 138.90, 138.95 and 139.06 (C arom). HRMS: calcd. for C32H40O5 (Mþ)
m=e 504.2877; found for (M þ 1)þ m=e 505.2957.
3,4,6-Tri-O-benzyl-2-deoxy-b-D-glucopyranosyl)carbonitrile (5a)
The compound was obtained from 5 (0.100 mmol, 56.6 mg) by method B in
20
91% yield (40.4 mg). Rf 0.81 (diethyl ether–hexane, 1:2); ½aꢄD þ 15.7 (c 0.470, CHCl3);
1H NMR (d, ppm): 1.99 [q, J1,2a ¼ 12.3, J2a,2b ¼ 12.6, J2a,3 ¼ 13.3, 1H, H(2a)], 2.43
[ddd, J2a,2b ¼ 12.6, J2b,3 ¼ 4.0, J1,2b ¼ 2.2, 1H, H(2b)], 3.40 [m, 1H, H(5)], 3.57 [t,
J3,4 ¼ J4,5 ¼ 8.8, 1H, H(4)], 3.63 [m, J3,2a ¼ 13.3, J3,2b ¼ 4.0, J3,4 ¼ 8.8, 1H, H(3)],
3.72 [m, 2H, H(6ab)], 4.21 [dd, J1,2a ¼ 12.3, J1,2b ¼ 2.2, 1H, H(1)], 4.56 and 4.63
(two d, JAB ¼ 12.2, 2H, CH2Ph), 4.57 and 4.89 (two d, JAB ¼ 10.8, 2H, CH2Ph),
4.64 and 4.71 (two d, JAB ¼ 11.7, 2H, CH2Ph), 7.30 (m, 15H, H arom); 13C NMR
(d, ppm): 35.31 (CH2), 63.88 (CHCN), 68.83, 72.14, 73.84 and 75.51 (4 groups
OCH2), 77.22, 79.41 and 80.24 (3 groups OCH), 117.15 (CN), 127.95, 128.00,
128.09, 128.13, 128.19, 128.23, 128.67, 128.78, 137.99, 138.06, and 138.17 (C arom).
HRMS calcd. for C28H29NO4 (Mþ) m=e 443.2098; found (M þ 1)þ m=e 444.2164.
3-(3,4,6-Tri-O-benzyl-2-deoxy-b-D-glucopyranosyl)-1-propene (6a)
The compound was obtained from 6 (0.100 mg, 58.1 mg) by method B in 90%
20
yield (41.3 mg). Rf 0.43 (diethyl ether–hexane, 1:2); ½aꢄD þ 2.73 (c 0.440, CHCl3); 1H

1198
M. HAN AND I. P. SMOLIAKOVA
NMR (d, ppm): 1.40 [q, J2a,2b ꢅ J2a,1 ꢅ J2a,3 ꢅ 11.7, 1H, H(2a)], 2.16 [br. dd,
J2a,2b ¼ 11.7, J2b,3 ¼ 4.9, 1H, H(2b)], 2.26 [m, 1H, H(7a)], 2.45 [m, 1H, H(7b)], 3.40
[m, 2H, H(1), H(3)], 3.48 [t, J3,4 ¼ J4,5 ¼ 9.4, H(4)], 3.65 [m, J4,5 ¼ 9.4, J5,6a ¼ 11.5,
J5,6b ¼ 3.5, 1H, H(5)], 3.73 [m, J5,6a ¼ 11.5, J5,6b ¼ 3.5, 2H, H(6ab)], 4.56 and 4.62
(two d, JAB ¼ 12.2, 2H, CH2Ph), 4.58 and 4.67 (two d, JAB ¼ 12.2, 2H, CH2Ph),
4.62 and 4.71 (two d, JAB ¼ 11.7, 2H, CH2Ph), 5.10 [m, 2H, H(9), H(10)], 5.82 [m,
13
=
1H, H(8)]. C NMR (d, ppm): 36.48 (CH2), 40.27 (CH2-CH CH2), 69.74, 71.56,
73.62, and 75.28 (4 groups OCH2), 75.19, 78.80, 79.26, and 81.35 (4 groups
OCH), 117.36 (H2C¼CH), 134.71 (HC¼CH2), 127.70, 127.77, 127.82, 127.93,
128.01, 128.10, 128.16, 128.52, 128.59, 138.63, 138.72 and 138.85 (C arom). HRMS
calcd. for C30H34O4 (Mþ) m=e 458.2458; found for (M þ 1)þ m=e 459.2526.
2-(3,4,6-Tri-O-benzyl-2-deoxy-b-D-glucopyranosyl)-
1-(Trimethylsilyl)ethanol (7a)
The compound was obtained from 7 (0.100 mmol, 65.5 mg) using method B in
35% yield (18.7 mg). 1H NMR (d, ppm): 0.27 (s, 9H, SiMe3), 1.45–1.6 [m, 2H, H(2a0),
H(2a)], 1.83 [m, 1H, H(2b0)], 2.17 [ddd, J2a,2b ¼ 12.5, J2b,3 ¼ 5.0, J1,2b ¼ 1.6, 1H,
H(2b)], 3.45–3.72 [m, 7H, H(1), H(3), H(4), H(5), H(6ab), H(10)], 4.63 and 4.71
(two d, JAB ¼ 11.7, CH2Ph), 4.55 and 4.90 (two d, JAB ¼ 10.8, CH2Ph), 4.52 and
4.57 (two d, JAB ¼ 12.7, CH2Ph), 7.30 (m, 15H, H arom); 13C NMR (d, ppm):
ꢃ3.91 (SiMe3), 29.96 (CH3), 37.58 (CH2), 66.56 (COH), 69.89, 71.70, 73.76 and
75.34 (4 groups OCH2), 78.64, 79.05, 80.26 and 80.93 (4 groups OCH), 127.85,
127.89, 128.14, 128.29, 128.61, 128.68, 138.35, 138.59 and 138.77 (C arom). HRMS
calcd. for C32H43SiO5 (M þ 1) m=e 535.2881; found (M þ 1)þ m=e 535.2904.
ACKNOWLEDGMENT
The authors gratefully acknowledge the University of North Dakota for
financial support.
REFERENCES
1. (a) Hultin, P. Bioactive C-glycosides from bacterial secondary metabolism. Curr. Topics
Med. Chem. 2005, 5, 1299–1331; (b) Levy, D. E.; Tang, C. The Chemistry of C-Glycosides;
Elsevier Science: Tarrytown, NY, 1995; (c) Postema, M. H. D. C-Glycoside Synthesis;
CRC Press: Boca Raton, FL, 1995.
2. He, L.; Zhang, Y. Z.; Tanoh, M.; Chen, G.-R.; Praly, E.-P.; Chrysina, E. D.; Tiraidis, C.;
Kosmopoulou, M.; Leonidas, D. D.; Oikonomakos, N. G. In search of glycogen phos-
phorylase inhibitors: Synthesis of C-D-glycopyranosylbenzo(hydro)quinines—Inhibition
of and binding to glycogen phosphorylase in the crystal. Eur. J. Org. Chem. 2007,
596–606.
3. Postema, M. H. D.; Maarten, H. D.; Piper, J. L.; Betts, R. L. Synthesis of stable
carbohydrate mimetics as potential glycotherapeutics. Synlett 2005, 1345–1358.
4. Levy, D. E.; Fugedi, P. Organic Chemistry of Sugars; CRC Press: Boca Raton, FL, 2005.
¨
5. Smoliakova, I. P. Synthesis of C-glycosylic compounds using three-membered cyclic
intermediates. Curr. Org. Chem. 2000, 4, 589–608.

2-ARYLTHIO-b-C-D-GLUCOPYRANOSIDES
1199
6. Smoliakova, I. P.; Caple, R.; Gregory, D.; Smit, W. A.; Shashkov, A. S.; Chizhov, O. S.
Highly selective formation of a b-C-glucosidic bond in the reactions of ArSCl-glucal
adducts with silicon-containing nucleophiles. J. Org. Chem. 1995, 60, 1221–1227.
7. Smoliakova, I. P.; Han, M.; Gong, J.; Caple, R.; Smit, W. A. Reactions of vinyl ethers
with ArSCl adducts of D-glucal. Tetrahedron 1999, 55, 4559–4572.
8. Pettit, G. R.; van Tamelen, E. E. Desulfurization with Raney nickel. In Organic Reactions;
A. C. Cope, (Ed.); John Wiley & Sons: New York, 1962; vol. 12; pp. 356–529.
9. Franck, R. W.; Marzabadi, C. H. Novel bicylic donors for the synthesis of 2-deoxy-b-
glycosides. J. Org. Chem. 1998, 63, 2197–2208.
10. Hashimoto, S.; Yanagiya, Y.; Honda, T.; Ikegami, S. A stereocontrolled construction of
2-deoxy-b-glycosidic linkages via 1,2-trans-b-glycosidation of 2-deoxy-2-[(p-methoxyphe-
nyl)thio]glycopyranosyl N,N,N0,N0-tetramethylphosphoroamidates. Chem. Lett. 1992,
1511–1514.
11. Yadav, J. S.; Baishya, G.; Dash, U. Synthesis of (þ)-amberketal and its analog from
L-abietic acid. Tetrahedron 2007, 63, 9896–9902.
12. Quintard, J. P.; Pereyre, M. Stereochemistry of the tributyltin hydride reduction of
cyclohexanones. Bull. Soc. Chim. Fr. 1972, 1950–1955.
13. Mozingo, R. Catalyst, Raney nickel, W-2. Org. Synth. Coll. 1955, 3, 181–183.

Copyright of Synthetic Communications is the property of Taylor & Francis Ltd and its content may not be
copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written
permission. However, users may print, download, or email articles for individual use.