A general procedure for conversion of S-glycosyl isothiourea derivatives into thioglycosides, thiooligosaccharides and glycosyl thioesters

Article abstract of DOI:10.1055/s-2001-11443

A simple procedure for conversion of S-glycosyl isothiourea derivatives into thioglycosides by promotion with triethylamine is described. The reaction conditions allow the synthesis of glycosyl thioesters and some thioglycosides, which cannot be prepared using the traditional approach. The procedure has been successfully applied for preparation of thiooligosaccharides, shown by syntheses of methyl 4-thio-α-cellobioside and methyl 4-thio-α-lactoside derivatives.

Full text of DOI:10.1055/s-2001-11443

PAPER
419
A General Procedure for Conversion of S-Glycosyl Isothiourea Derivatives
into Thioglycosides, Thiooligosaccharides and Glycosyl Thioesters
a*
b
b
Farid M. Ibatullin, Stanislav I. Selivanov, Alexander G. Shavva
aMolecular and Radiation Biophysics Division, Petersburg Nuclear Physics Institute, Gatchina, 188300, Russia
Tel +(7)8127146056; Fax +(7)8127132303; E-mail: ibatullin@omrb.pnpi.spb.ru
bChemical Department of Petersburg State University, St.-Petersburg, Russia
Received 22 September 2000; revised 10 November 2000
thiols. Using this approach, thioglycosides were prepared
starting from 1,2-trans-glycosyl esters, trichloroacetimi-
Abstract: A simple procedure for conversion of S-glycosyl isothio-
urea derivatives into thioglycosides by promotion with triethy-
lamine is described. The reaction conditions allow the synthesis of
7
8
9
dates, 1-O-trimethylsilyl glycosides, and from glycopy-
glycosyl thioesters and some thioglycosides, which cannot be pre- ranoses.10 Thioglycosides were also prepared from
1
1
pared using the traditional approach. The procedure has been suc- carbohydrate sulfenates and by free-radical addition of
-thiosugars to alkenes.12 Very recently, synthesis of
cessfully applied for preparation of thiooligosaccharides, shown by
syntheses of methyl 4-thio- -cellobioside and methyl 4-thio- -lac-
toside derivatives.
1
alkyl- and arylthioglycosides via thioiminium salts using
13
phase transfer conditions was described.
Key words: alkyl halides, carbohydrates, thioglycosides, thiooli-
One of the most convenient and simple methods for the
preparation of thioglycosides utilizes isothiourea deriva-
tives of sugars as starting materials, which are readily
available from the glycosyl halides and thiourea.14 With
this method thioglycosides can be synthesized at very
mild conditions without the use of malodorous and toxic
mercaptans. Generally, the synthetic procedure involves a
cleavage of a glycosyl isothiouronium salt by treatment
with potassium carbonate and sodium hydrogensulfite or
metabisulfite in water/acetone media, followed by reac-
gosaccharides, thioesters
Thioglycosides are a very important class of sugar deriv-
atives. They are widely employed as inhibitors, inducers
1
2
3
and ligands for affinity chromatography of carbohydrate
processing enzymes and proteins. The protected thiogly-
cosides have found a wide application in synthetic carbo-
hydrate chemistry as very convenient, versatile
glycosylation agents, due to their stability during various
chemical transformations and their ability to be readily
tion of the resulting acetylated 1-thioglycose with alkyl
15
(
aryl) halide. Often, the thioglycoses are isolated before
4
converted into a variety of other functionalities.
the alkylation, but that approach is more laborious and has
Several methods have been published for the synthesis of no advantages comparing with the one-pot procedure.
thioglycosides. The most common include a reaction of a
glycosyl halide with a thiolate anion or a reaction of a
Despite its obvious simplicity, the method is not free from
3
b,5
some drawbacks. Often, homogeneous reaction condi-
tions can be reached only at low concentration of the re-
agents due to a poor solubility of concentrated aqueous
6
1
-thio-glycopyranose with an alkyl halide . Other meth-
ods are based on Lewis acid catalyzed glycosylation of
OAc OAc
O
3 R=Et
4 R=4-NO2Bn
S
AcO
R
OAc
OAc
ii
NO2
S
O
AcO
AcO
R1
OAc
R1
OAc
ii
ii
OAc
5
O
R2
AcO
O
R2
AcO
NO2
i
S
NH
OAc
AcO
OAc
HBr
NH2
O
Br
AcO
AcO
1
2
1
2
R =H, R =OAc
S
1
2
ii
R =OAc, R =H
OAc
6
OAc
O
AcO
AcO
S
CH3
OAc
7
O
Reagents and conditions: i), thiourea, MeCN, reflux for 10 min; ii) Et N, alkyl halide or aryl fluoride (or Ac O for 7), r.t., 10 min 2 h.
3
2
Scheme 1
Synthesis 2001, No. 3, 419–422 ISSN 0039-7881 © Thieme Stuttgart · New York

4
20
F. M. Ibatullin et al.
PAPER
K CO in organic phase. Moreover, the presence of water Recently, it was shown that the triphenylmethyl group
2
3
in the reaction mixture does not allow the use of water- provides reliable protection of the thio group of 1-thioal-
sensitive alkylation and acylation agents, thus limiting a doses, stable during various chemical transformations and
may be selectively removed at mild conditions.1 Due to
this fact, triphenylmethyl 1-thioglycopyranosides have
proven to be very valuable for synthesis of
8a
range of application of the method.
Herein, we wish to report a novel procedure for synthesis
of thioglycosides by simple treatment of glycosyl isothio-
urea derivatives with triethylamine and appropriate aryl or
thiooligosacharides1 and -glucosinolates.
c,16
18b
alkyl halide in acetonitrile. We have found that the utiliza- Due to the high sensitivity of trityl halides to hydrolysis,
tion of alkylamines instead of K CO allows the transfor- the synthesis of the corresponding derivatives requires an-
2
3
mation in anhydrous homogeneous conditions hydrous reaction conditions that can not be achieved by
irrespective of the reactant concentrations.
the former one-pot approach. Using our method, we have
synthesized triphenylmethyl 2,3,4,6-tetra-O-acetyl-1-
thio- -D-glucopyranoside (6) in 51% yield by reaction of
compound 1 with trityl chloride for 2 hours. For compar-
ison, triphenylmethyl 2-acetamido-3,4,6-tri-O-acetyl-1-
thio- -D-glucopyranoside was prepared in 42% yield by
treatment of the corresponding thioglycose with trityl
chloride in dry pyridine for 4 days.19
Alkylamines are strong bases, therefore they readily react
with the isothiouronium salts affording 1-thioaldoses.
Furthermore, because alkylamines are weaker nucleo-
philes than thiols, they can be successfully used for the ac-
tivation of the resulting thioaldoses by the converting
them into more nucleophilic thiolate anions. Various
mono-, di- and trialkylamines may be used for synthesis
of thioglycosides by the described procedure, but less ba- Similarly, glycosyl isothiourea derivatives can be trans-
sic amines, for example pyridine, are not able to cleave formed into glycosyl thioesters, another important class of
glycosyl isothiouronium salts.
carbohydrate derivatives, which has also found a wide ap-
plication in the synthesis of thiooligosacharides. Thus,
treatment of 1 with triethylamine and acetic anhydride af-
2
0
The reaction proceeds smoothly at room temperature af-
fording products in high yields. A series of thioglycosides
of mono- and disaccharides have been prepared using the
procedure; the synthesis of some are described herein
forded 1-thioacetate 7 in a good yield. This approach is a
good alternative to the existing methods1
4c,21
of preparing
glycosyl thioesters because of its simplicity and availabil-
(
Scheme 1).
ity of chemicals.2
2,23
The reaction time in most cases does not exceed 2 hours.
Starting isothiourea derivatives can be prepared separate-
ly or in situ from the appropriate glycosyl halide and thio-
urea in the same solvent.
Despite the fact that a direct one-pot conversion of S-gly-
cosyl isothiourea derivatives into thioglycosides is well
described, the only case where such an approach for thioo-
ligosaccharide preparation is used is in the synthesis of
Several solvents have been tested for the reaction. Al-
though the transformation in DMF is faster, acetonitrile
has proven to be suitable for most syntheses of thioglyco-
sides and lower thiooligosaccharides, whereas DMF is
preferred for synthesis of longer thiooligosaccharides,16
mainly because of the solubility problems.
24
4
-thiolactosylceramide. The synthesis was performed by
reaction of the corresponding triflate with 5-fold excess of
isothiouronium salt in acetone/methanol mixture using
K CO as a promoter.
2
3
Now, we describe a preparation of methyl 4-thiolactoside
9) and methyl 4-thiocellobioside (10) derivatives using
(
As described previously, isothiourea derivatives of sugars
can be successfully applied for synthesis of nitrophenyl
the new procedure(Scheme 2). Compounds 10 and 9 were
prepared respectively from 1 and 2 in high yields by tri-
ethylamine promoted reaction with slight excess
1
-thioglycosides by reaction with nitrofluorobenzenes in
17
acetone/water mixture in the presence of K CO . How-
2
3
(
1.1 equivalents) of methyl 2,3,6-tri-O-benzoyl-4-O-tri-
ever, the authors reported that the direct synthesis of
thioglycosides using in situ cleavage of the isothiouroni-
um salts required considerable time (24 hours) for com-
pletion. We have found that the reaction of
isothiouronium bromide 1 with triethylamine and
fluoromethanesulphonyl- -D-galactopyranoside (8). In-
terestingly, the previous attempt to synthesize compound
9
by coupling the sodium salt of 1-thio -D-galactopyra-
25
nose with triflate 8 in HMPA was not successful.
In conclusion, a facile general procedure has been devel-
oped for the conversion of isothiourea derivatives of sug-
ars into thioglycosides, thiooligosaccharides and glycosyl
thioesters. We believe that the described approach may
serve as a practical and convenient alternative to currently
available methods for the synthesis of these types of com-
pounds.
2
1
,4-dinitrofluorobenzene in acetonitrile was completed in
0 minutes affording 2,4-dinitrophenylthio glucopyrano-
side 5 in 78% yield.
OBz
R1
OAc
OMe
TfO
BzO
O
O
O
BzO
S
2
1
or 2
R
BzO
AcO
BzO
OMe
OAc
NMR spectra were recorded on a Bruker spectrometer DPX-300
OBz
1
2
1
13
8
9 R =OAc, R =H
(300 MHz and 75.47 MHz for H and C, respectively). Chemical
shifts ( ) are given in ppm relative to the signal for internal TMS for
1
2
10 R =H, R = OAc
1
13
H, and CDCl ( = 77.03 ppm) for C. MeCN was distilled over
3
Scheme 2
Synthesis 2001, No. 3, 419–422 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
A General Procedure for Conversion of S-Glycosyl Isothiourea Derivatives
421
P O . Glycosyl bromides were prepared according to the described
work up, the product was crystallized from i-PrOH and recrystal-
lized from the same solvent. Yield: 50%; mp: 182 183 C;
2
5
2
6
procedures. Methyl 2,3,6-tri-O-benzoyl-4-O-trifluoromethane-
sulphonyl- -D-galactopyranoside (8) was prepared as described in
ref 27 and recrystallized from i-PrOH. Mps are uncorrected.
2
0
[ ]D
= 2.0° (c 1.0, CHCl3).
1H NMR (CDCl3): = 1.92, 1.93, 1.94, 2.04 (4 s, each 3H, 4
CH CO), 2.88 (td, 1H, J = 4.6 Hz, J5,6b = 2.2 Hz, H-5), 3.74 (dd,
3
5,6a
General Procedure
To a stirring suspension of a S-glycosyl isothiouronium bromide,
prepared by refluxing (10 min) a solution of a glycosyl bromide
1
H, H-6b), 3.76 (d, 1H, J = 10.0 Hz, H-1), 4.00 (dd, 1H, J6a,6b = 12,6
Hz, H-6a), 4.92 (dd, 1H, J4,5 = 9.3 Hz, H-4), 4.97 (dd, 1H, J3,4 = 9.4
Hz, H-3), 5.09 (dd, 1H, J2,3 = 10.0 Hz, H-2), 7.18 7.42 [m, 15H,
(
10 mmol) and thiourea (0.8 g, 10.5 mmol) in MeCN (10 20 mL),
(
C H ) C].
6 5 3
Et N (20 25 mmol) and alkyl halide (10 15 mmol) were added at
3
13
C NMR (CDCl ): = 20.1, 20.2, 20.3, 20.4 (4 CH -Ac), 61.4 (C-
3
3
r.t. The reaction mixture was stirred until reaction completion (con-
trol by TLC) and concentrated at reduced pressure. The residue was
dissolved in CH Cl (50 mL), the solution washed with H O (2 30
6
), 67.8 (C-4), 68.4 (CPh ), 69.3, 73.9, 74.9 (C-2, C-3, C-5), 83.2
3
(
C-1), 126.6, 127.4, 129.6, 143.9 (C H ), 168.9, 169.9, 170.2 (4
6 5
2
2
2
CO-Ac).
mL), dried (MgSO ), and concentrated. The residue was crystal-
4
lized from hexane and recrystallized from appropriate solvent.
MS: m/z = 629.7 (M+Na).
Ethyl 2,3,4,6-Tetra-O-acetyl-1-thio- -D-galactopyranoside (3)
Prepared from S-galactopyranosyl isothiouronium bromide (2) and
Anal. Calcd for C H O S: C, 65.33; H, 5.65. Found: C, 65.28; H,
33 34 9
5.72.
,3,4,6-Tetra-O-acetyl-1-S-acetyl-1-thio- -D-glucopyranose (7)
Prepared by treatment of 1 (10 mmol) in MeCN (20 mL) with Et N
ethyl bromide (1.3 equiv), isolated yield: 72%; mp: 75 76
C
=
2
5d
20
15d
20
(
Lit.1 mp: 75 C); [ ]D
= 7.9° (c 1.0, CHCl ) {Lit. [ ]D
3
3
7
.8° (c 2.5, CHCl )}.
3
(
4.18 mL, 30 mmol) and acetic anhydride (2.36 mL, 25 mmol). Stir-
1H NMR CDCl3 : = 1.28 (t, 3H, SCH Me), 1.97, 2.03, 2.06, 2.14
ring for 1 h at r.t., usual work-up, and recrystallization from EtOH
2
2
1a
(
4
s, each 3H, 4 CH CO), 2.73 (m, 2H, J = 7.4 Hz, SCH Me),
afforded the pure product (3.0 g, 74%); mp: 118 119 C (Lit. mp:
3
2
2
0
21a
20
3
.92 (dt, 1H, J5,6 = 6.6 Hz, H-5), 4.12 (m, 2H, H-6ab), 4.48 (d, 1H,
118 C); [ ]D = +9.8° (c 1.0, CHCl ) {Lit. [ ]D = +10.7° (c
3
J1,2 = 9.9 Hz, H-1), 5.04 (dd, 1H, J3,4 = 3.3 Hz, H-3), 5.23 (dd, 1H,
J2,3 = 10.0 Hz, H-2), 5 42 dd 1H J4 5 < 1 Hz, H-4).
1.496, CHCl )}.
3
Anal. Calcd for C H O S: C, 47.29; H, 5.46. Found: C, 47.35; H,
5.39.
1
6
22 10
1
3C NMR (CDCl3): = 14.7 (CH -Et), 20.4, 20.5, 20.6 (4 CH3-
3
Ac), 24.2 (CH -Et), 61.3 (C-6), 67.0, 67.1, 71.8, 74.3 (C-2, C-3, C-
2
Methyl 2,3,6-Tri-O-benzoyl-4-S-(2,3,4,6-tetra-O-acetyl- -D-ga-
lactopyranosyl)-4-thio- -D-glucopyranoside (9)
4
, C-5), 83.9 (C-1), 169.4, 169.9, 170.1, 170.2 (4 CO-Ac).
p-Nitrobenzyl 2,3,4,6-Tetra-O-acetyl-1-thio- -D-galactopyrano-
side (4)
Prepared by treatment of 2 with triflate 8 (10% excess) for 60 min
under the described conditions. After usual work up and crystalliza-
tion from i-PrOH, the product was isolated in 70% yield. From the
mother liquor, an additional amount of the product (9%) was ob-
tained by column chromatography. Mp: 128 129 C (EtOH);
[ ]D = +64.7° (c 1.0, CHCl3).
1H NMR (CDCl3): = 1.57, 1.92, 2.04, 2.08 (4 s, 12H, 4
Prepared from 2 and p-nitrobenzyl chloride (1 equiv). After 10 min
TLC showed complete conversion. Usual work up and recrystalli-
1
5e
zation from EtOH afforded 4 in 78% yield; mp: 95 96 C (Lit.
2
0
15e
22
20
mp: 94 95 C); [ ]D
7.6° (c 0.5, CHCl )}.
=
77.3° (c 0.5, CHCl ) {Lit. [ ]D
=
3
8
3
1
H NMR (CDCl ): = 1.97, 2.05, 2.06, 2.16 (4 s, each 3H, 4
CH CO), 3.30 (dd, 1H, J = 11.1 Hz, H-4), 3.44 (s, 3H, CH O),
3
3
4,5
3
CH CO), 3.88 (td, 1H, J = 6.6 Hz, H-5), 4.00 (m, 2H, H-6ab),
3.92 (td, 1H, J5 ,6 a = 6.77 Hz, J5 ,6 b = 6.26 Hz, H-5 ), 4.00 (dd, 1H,
H-6 b), 4.04 (dd, 1H, J6a ,6b = 11.4 Hz, H-6 a), 4.39 (td, 1H,
J5,6a = 4.0 Hz, J5,6b = 2.0, H-5), 4.79 (dd, 1H, H-6b), 4.87 (dd, 1H,
J6a,6b = 12.0 Hz, H-6a), 4.93 (d, 1H, J1 2 = 9.9 Hz, H-1 ), 4.99 (dd,
1H, J3 ,4 = 3.4 Hz, H-3 ), 5.08 (dd, 1H, J2 3 = 9.9 Hz, H-2 ), 5.18 (d,
1H, J1,2 = 3.6 Hz, H-1), 5.22 (dd, 1H, J2,3 = 9.6 Hz, H-2), 5.39 (dd,
3
5,6
3
.91, 4.04 (2 d, each 1H, J = 13.1 Hz, SCH ), 4.33 (d, 1H,
2
J1,2 = 9.9 Hz, H-1), 5.00 (dd, 1H, J3,4 = 3.6 Hz, H-3), 5.29 (dd, 1H,
J2,3 = 10.0 Hz, H-2), 5.42 (dd, 1H, J4,5 = 0.7 Hz, H-4), 7.49, 8.19 (2
d, each 2H, J = 7.0 Hz, C H NO ).
6
4
2
1
3C NMR (CDCl3): = 20.4, 20.5, 20.55, 20.6 (4 CH -Ac), 32.7
3
1
8
H, J4 ,5 = 1.0 Hz, H-4 ), 6.00 (dd, 1H, J3,4 = 11.1 Hz, H-3), 7.36
(
CH -Bn), 61.3 (C-6), 66.8, 67.1, 71.5, 74.6 (C-2, C-3, C-4, C-5),
2
.11 (m, 15H, 3 C H CO).
6
5
8
1
2.4 (C-1), 123.7, 129.9, 144.8, 147.1 (C H ), 169.5, 169.8, 169.9,
70.2 (4 CO-Ac).
6 4
1
3
C NMR (CDCl ): = 19.9, 20.4, 20.5, 20.6 (4 CH -Ac), 46.3 (C-
3 3
4
7
), 55.6 (CH -O), 61.3, 63.8 (C-6 , C-6), 66.7, 66.9, 67.4, 69.4, 71.6,
3.2, 74.0 (C-2, C-2 , C-3, C-3 , C-4 , C-5, C-5 ), 81.9 (C-1 ), 97.2
3
Anal. Calcd for C H NO S: C, 50.50; H, 5.04; N, 2.80. Found: C,
21
25
11
5
0.57; H, 5.11; N, 2.73.
(
C-1), 128.3, 128.4, 129.2, 129.5, 129.7, 129.8, 133.2 (C H ), 165.5,
6 5
2
,4-Di-nitrophenyl 2,3,4,6-Tetra-O-acetyl-1-thio- -D-glucopyr-
1
65.7, 166.0 (3 CO-Bz), 169.4, 169.7, 170.1, 170.2 (4 CO-Ac).
anoside (5)
MS: m/z = 875.8 (M+Na).
Prepared by reaction of 2,4-di-nitrofluorobenzene (1 equiv) with
corresponding isothiouronium bromide under described conditions.
According to TLC, the reaction was completed in 10 min. Usual
work up and recrystallization from EtOH afforded 5 in 78% yield;
Anal. Calcd for C H O S: C, 59.15; H, 5.20. Found: C, 59.23; H,
5.29.
4
2
44 17
Methyl 2,3,6-Tri-O-benzoyl-4-S-(2,3,4,6-tetra-O-acetyl- -D-glu-
copyranosyl)-4-thio- -D-glucopyranoside (10)
Prepared from 1 using the procedure described for 9 in 80% yield;
mp: 197 198 C (EtOH) (Lit. mp: 185 188 C); [ ]D = +60.5°
(c 1.1, CHCl ) {Lit. [ ] = +62° (c 1.4, CHCl )}. The NMR data
1
7
20
mp: 202 203 C (Lit. mp: 203 204 C); [ ]D
=
93.0° (c 1.1,
17
20
CHCl ) {Lit. [ ]
= 96.0° (c 0.5, CHCl )}. The NMR data were
in full agreement with published values.
3
D
3
1
7
3d
20
3
d
20
Anal. Calcd for C H N O S: C, 45.28; H, 4.18; N, 5.28. Found:
2
0
22
2
13
3
D
3
3
d
C, 45.28; H, 4.11; N, 5.20.
were in full agreement with published values.
Triphenylmethyl 2,3,4,6-Tetra-O-acetyl-1-thio- -D-glucopyra-
noside (6)
Prepared by treatment of 1 with trityl chloride under the described
conditions. The reaction mixture was kept for 2 h at r.t. After usual
Acknowledgement
We are grateful to Dr. Hugues Driguez for fruitful discussions.
Synthesis 2001, No. 3, 419–422 ISSN 0039-7881 © Thieme Stuttgart · New York

4
22
F. M. Ibatullin et al.
PAPER
Eisele, T.; Toepfer, A.; Kretzschmar, G.; Schmidt, R. R.
Tetrahedron Lett. 1996, 37, 1389.
Eisele, T.; Windmuller, R.; Schmidt, R. R. Carbohydr. Res.
References
(
1) a) Brajeswar, P.; Walter, K.; Carbohydr. Res. 1984, 126, 27.
b) Kuhn, C. -S.; Lehmann, J.; Steck, J. Tetrahedron 1990, 46,
1998, 306, 81.
3
129.
(
9) Li, Z. –J.; Liu, P. -L.; Li, Z. –J.; Qiu, D. -X.; Cai, M. -S. Synth.
Commun. 1990, 20, 2169.
c) Blanc-Muesser, M.; Vigne, L.; Driguez, H.; Lehmann, J.;
Steck, J.; Urbahns, K. Carbohydr. Res. 1992, 224, 59.
d) Apparu, C.; Driguez, H.; Williamson, G.; Svensson, B.
Carbohydr. Res. 1995, 277, 313.
(
10) Li, P.; Sun, L.; Landry, D.W.; Zhao, K. Carbohydr. Res. 1995,
75, 179.
2
(
(
11) Fokt, I.; Szeja, W. Carbohydr. Res. 1992, 232, 169.
12) Lacombe, J. M.; Rakotomanomana, N.; Pavia, A. A.
Tetrahedron Lett. 1988, 29, 4293.
13) Fujihira, T.; Takido, T.; Seno, M. J. Mol. Catalysis A:
Chemical 1999, 137, 65.
e) Marino, C.; Marino, K.; Miletti, L.; Manso Alves, M. J.;
Colli, W.; de Lederkremer, R. M. Glycobiology 1998, 8, 901.
2) Rho, D.; Desrochers, M.; Jurasek, L.; Driguez, H.; Defaye, J.
J. Bacteriol. 1982, 149, 47.
(
(
(
Defaye, J.; Guillot, J. M.; Biely, P.; Vrsanska, M. Carbohydr.
Res. 1992, 228, 47.
Birk, R.; Ikan, A.; Bravdo, B.; Braun, S.; Shoseyov, O. Appl.
Biochem. Biotechnol. 1997, 66, 25.
(
14) a) Horton, D. Methods in Carbohydrate Chemistry 1963, 2,
4
33; and references therein.
b) Bonner, W. A.; Kahn, J. E. J. Am. Chem. Soc. 1951, 73,
241.
2
3) a) Alhadeff, J. A.; Miller, A. L.; O’Brien, J. S. Anal. Biochem.
c) Horton, D.; Wolfrom, M. L. J. Org. Chem. 1962, 27, 1794.
d) Chipowsky, S.; Lee, Y. C. Carbohydr. Res. 1973, 31, 339.
15) a) Èerný, M.; Pacák, J. Chem. Listy 1958, 52, 2090.
b) Èerný, M.; Pacák, J. Collect. Czech. Chem. Commun. 1959,
1
974, 60, 424.
b) Matta, K. L.; Girotra, R. N.; Barlow, J. J. Carbohydr. Res.
975, 43, 101.
c) Schnaar, R. L.; Lee, Y. C. Biochemistry 1975, 14, 1535.
d) Orgeret, C.; Seillier, E.; Gautier, C.; Defaye, J.; Driguez, H.
Carbohydr. Res. 1992, 224, 29.
(
1
2
4, 2566.
c) Èerný, M.; Pacák, J. Collect. Czech. Chem. Commun. 1961,
6, 2084.
d) Èerný, M.; Stanìk, J.; Pacák, J. Monatsh. Chem. 1963, 94,
90.
e) Claeyssens, M.; De Bruyne, C. K.; Carbohydr. Res. 1972,
2, 460.
2
(
4) Review: a) Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93,
1
503; and references therein.
Review: b) Garegg, P. J. Adv. Carbohydr. Chem. Biochem.
997, 52, 179; and references therein.
c) Nilsson, S.; Lonn, H.; Norberg, T. Glycoconjugate J. 1989,
, 21.
d) Kihlberg, J.; Bundle, D. R. Carbohydr. Res. 1991, 216, 67.
e) Hasegawa, A.; Adachi, K.; Yoshida, M.; Kiso, M.
Carbohydr. Res. 1992, 230, 257.
f) Hasegawa, A.; Ando, T.; Kato, M.; Ishida, H.; Kiso, M.
Carbohydr. Res. 1994, 257, 55.
g) Fukase, K.; Hasuoka, A.; Kinoshita, I.; Aoki, Y.;
Kusumoto, S. Tetrahedron 1995, 51, 4923.
2
1
2
(
16) Ibatullin, F. M.; Utille, J. -P.; Cottaz, S.; Mori, H.; Svensson,
B.; Driguez, H. 3-d International Carbohydrate
Bioengineering Meeting, Newcastle Upon Tyne, Great
Britain, April 11 14, 1999.
17) Driguez, H.; Szeja, W. Synthesis 1994, 1413.
18) a) Blanc-Muesser, M.; Vigne, L.; Driguez, H. Tetrahedron
Lett. 1990, 31, 3869.
b) Blanc-Muesser, M.; Driguez, H.; Joseph, B.; Viaud, M. C.;
Rollin, P. Tetrahedron Lett. 1990, 31, 3867.
19) Paul, B.; Korytnyk, W. Carbohydr. Res. 1984, 126, 27.
20) Review: Driguez, H. Top. Curr. Chem. 1997, 187, 85; and
references therein.
Schou, C.; Rasmussen, G.; Schulein, M.; Henrissat, B.;
Driguez, H. J. Carbohydr. Chem. 1993, 12, 743.
21) a) Bonner, W. A. J. Am. Chem. Soc. 1951, 73, 2659.
b) Holland, C. V.; Horton, D.; Miller, M. J.; Bhacca, N. B. J.
Org. Chem. 1967, 32, 3077.
6
(
(
(
5) Review: Conchie, B. J.; Levvy, G. A.; Mrach, C. A. Adv.
Carbohydr. Chem. Biochem. 1957, 12, 157.
Conchie, B. J.; Levvy, G. A. Methods in Carbohydrate
Chemistry 1963, 2, 335.
(
(
Helferich, B.; Grunewald, H.; Landenhoff, F. Chem. Ber.
953, 86, 873.
Helferich, B.; Turk, D. Chem. Ber. 1956, 89, 2215.
Zinner, H.; Koine, A.; Nimz, H. Chem. Ber. 1960, 93, 2705.
Wagner, G.; Flegel, P. Arch. Pharm. (Weinheim Ger.) 1962,
1
(
(
c) Defaye, J.; Driguez, H.; Ohleyer, E.; Orgeret, C.; Viet, C.
Carbohydr. Res. 1984, 130, 317.
2
95, 430.
Apparu, M.; Blanc-Muesser, M.; Defaye, J.; Driguez, H. Can.
J. Chem. 1981, 59, 314.
Tsvetkov, Yu. E.; Byramova, N. E.; Backinovsky, L. V.
Carbohydr. Res. 1983, 115, 254.
22) Some acetylated 1-thio-glycopyranoses were prepared from
isothiouronium salts using the two-step procedure involving
23
cleavage of the S-amidino group, isolation of corresponding
1-thio-aldose, and subsequent re-acetylation for 18 h in pyri-
(
6) Durette, P. L.; Shen, T. Y. Carbohydr. Res. 1980, 81, 261.
Lee, R. T.; Lee, Y. C. Carbohydr. Res. 1982, 101, 49.
Hasegawa, A.; Morita, M.; Kojima, Y.; Ishida, H.; Kiso, M.
Carbohydr. Res. 1991, 214, 43.
dine.
(
(
23) Èerný, M.; Vrkos, J.; Stanìk, J. Collect. Czech. Chem.
Commun. 1959, 24, 64.
24) Albrecht, B.; Pütz, U.; Schwarzmann, G. Carbohydr. Res.
Defaye, J.; Guillot, J. M. Carbohydr. Res. 1994, 253, 185.
Contour-Galcera, M. O.; Guillot, J. M.; Ortiz-Mellet, C.;
Pflieger-Carrara, F.; Defaye, J.; Gelas, J. Carbohydr. Res.
1
995, 276, 289.
Wang, L. -X.; Lee, Y. C. J. Chem. Soc., Perkin Trans. 1 1996,
81.
5
1
996, 281, 99.
(
(
25) Reed, L. A.; Goodman, L. Carbohydr. Res. 1981, 94, 91.
26) Nicholas, S. D.; Smith, F. Nature 1948, 161, 349.
Haynes, L. J.; Newth, F. W. Adv. Carbohydr. Chem.
Biochem. 1955, 10, 207.
27) Blanc-Muesser, M.; Defaye, J.; Driguez, H. J. Chem. Soc.,
Perkin Trans. 1 1982, 15.
Contour-Galcera, M. O.; Ding, Y.; Ortiz-Mellet, C.; Defaye,
J. Carbohydr. Res. 1996, 281, 119.
Schwarzmann, G.; Hofmann, P.; Putz, U. Carbohydr. Res.
1
997, 304, 43.
(
(
7) Review: Horton, D.; Hutson, D. H. Adv. Carbohydr. Chem.
Biochem. 1963, 18, 123.
Lemieux, R.U.; Shyluk, W. P. Can. J. Chem. 1953, 31, 528.
8) Schmidt, R. R.; Stumpp, M. Liebigs Ann. Chem. 1983, 1249.
Andrews, J. S.; Pinto, B. M. Carbohydr. Res. 1995, 270, 51.
Article Identifier:
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