Synthesis of anomeric sulfimides and their use as a new family of glycosyl donors

Article abstract of DOI:10.1002/1099-0690(20021)2002:1<171::AID-EJOC171>3.0.CO;2-7

We introduce a convenient synthesis of anomeric sulfimides, the ability of which to act as glycosyl donors has been tested with various thiophilic reagents and acceptors.

Full text of DOI:10.1002/1099-0690(20021)2002:1<171::AID-EJOC171>3.0.CO;2-7

FULL PAPER
Synthesis of Anomeric Sulfimides and Their Use as a New Family
of Glycosyl Donors
[a]
[a]
[b]
[a]
´
´
Florence Chery, Stephanie Cassel, Hans Peter Wessel, and Patrick Rollin*
Dedicated to Professor Joachim Thiem on the occasion of his 60th birthday
Keywords: Anomeric sulfimides / Glycosyl donors / Glycosylations
We introduce a convenient synthesis of anomeric sulfimides, the ability of which to act as glycosyl donors has been tested
with various thiophilic reagents and acceptors.
syl-donating aptitude of the anomeric sulfimides has been
tested with various acceptors and thiophilic activators.
Introduction
Since the recognition of the biologically important role
Results and Discussion
of oligosaccharides, there has been an ongoing demand for
new and more efficient methods for their synthesis. Thus,
the development of stereoselective glycosylation reactions is
a longstanding topic in carbohydrate chemistry.[1] Thiogly-
cosides have attracted considerable attention in oligosacch-
aride synthesis over recent years, due to their stability under
various different chemical conditions and their versatility of
application.[2] The S-linked anomeric moiety may therefore
act as a temporary protective group, and can also be activ-
ated by various thiophilic reagents when required. These
interesting characteristics have given rise to the develop-
ment of miscellaneous anomeric thio derivatives including
xanthates[3] and sulfoxides.[4,5]
With the goal of developing a new family of thio-func-
tionalised glycosyl donors, we have investigated the syn-
thesis of carbohydrate-derived sulfimides.[6] These anomeric
sulfimides are analogues of the corresponding sulfoxides,
with the oxygen atom replaced by a substituted nitrogen
atom. Our first syntheses were carried out on various pro-
tected ethyl 1-thio-glucopyranosides. In this paper, the work
has been extended to different peracetylated thioglycosides
of -galactose, -mannose, -xylose, 2-amino-2-deoxy--
glucose, -rhamnose and -fucose. Furthermore, the glyco-
Sulfimide Synthesis
N-Tosylsulfimides are usually prepared by means of the
reaction between chloramine T (the sodium salt of N-
chloro-p-toluenesulfonamide) and sulfides in aqueous me-
dia, together with a cosolvent.[7] However, use of the aque-
ous system often results in significant formation of sulfox-
ides as by-products. Johnson and co-workers demonstrated
that sulfoxide formation could be minimized under phase-
transfer conditions.[8] By use of a similar methodology, it
has been possible to obtain anomeric N-tosylsulfimides eas-
ily by means of the reaction between alkyl thioglycosides
and chloramine T under phase-transfer catalysis conditions
(Scheme 1).
Scheme 1
Our syntheses were initially focused on a series of di-
versely protected ethyl 1-thio-β--glucopyranosides. These
turned out to be more reactive than their phenyl 1-thio
counterparts in the reaction with chloramine T. The latter
substrates gave only the corresponding sulfoxides, which
may be due to steric hindrance. The anomeric sulfimides
1Ϫ5 (Scheme 2) prepared from ethyl 1-thio-β--glucopyr-
anosides have been obtained in good yields (80Ϫ90%) and
with high stereoselectivity, achieving a de of Ͼ 90% in most
cases (Table 1).
[a]
Institut de Chimie Organique et Analytique, UMR 6005,
´
´
Universite d’Orleans,
´
B. P. 6759, 45067 Orleans, France,
Fax: (internat.) ϩ 33-2/38417281
E-mail: Patrick.Rollin@univ-orleans.fr
F. Hoffmann-La Roche Ltd., Pharma Division, Discovery
Chemistry, Dept. PRBC, Bldg. 92/7.92,
4070 Basel, Switzerland
[b]
E-mail: hans p.wessel@roche.com
Ϫ
Eur. J. Org. Chem. 2002, 171Ϫ180
WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
1434Ϫ193X/02/0101Ϫ0171 $ 17.50ϩ.50/0
171

´
F. Chery, S. Cassel, H. P. Wessel, P. Rollin
FULL PAPER
Scheme 2
Table 1. Sulfimides derived from variously protected ethyl 1-thio-
β--glucopyranosides
Scheme 3
responding oxazoline.[12] The formation of oxazolines from
N-acetylglucosamine is a well-known reaction that occurs
upon activation of the anomeric centre.[13]
[a]
1
Satisfactory spectroscopic data were obtained for all
de values were estimated by H NMR spectra.
1
compounds, and their H NMR spectra permitted estima-
tion of the product composition (i.e., the de values with
respect to the newly formed stereogenic centre at the sulfur
atom). The crystallisation of some anomeric sulfimides was
attempted, with the aim of establishing the absolute config-
uration at the sulfur atom by X-ray crystallography. This,
however, was severely hampered by their intrinsic instability
and was ultimately unsuccessful.
These encouragingly good yields and stereoselectivities
induced us to explore the scope of this reaction with further
carbohydrate compounds. Peracetylated alkyl 1-thio-glyco-
pyranosides derived from -galactose, -mannose, -xylose,
-fucose, -rhamnose, and -glucosamine were chosen, due
to the abundance of these sugars in naturally occurring oli-
gosaccharides. Generally, the sulfimides 6Ϫ15 (Scheme 3)
were obtained in good yields and with good stereoselectivit-
Glycosylation Reactions
In order to test their glycosyl-donating aptitudes and to
ies (Table 2). Only in some cases was the yield moderate, find suitable reaction conditions for glycosylation, the an-
due to concomitant sulfoxide formation. omeric sulfimides were submitted to various thiophilic ac-
The formation of sulfimide is believed to proceed through tivators, with different solvents and glycosyl acceptors. Pre-
an ionic mechanism, one feature of this being that the sul- liminary experiments focused on the activation of the per-
fonium intermediate may be intercepted by water to pro- O-benzylated -gluco sulfimide 4 as donor, with MeOH as
duce sulfoxides.[9] A possible source of water may originate a simple and reactive model acceptor and with use of
from incomplete removal of crystal water from chloramine Kahne-type activation.[4] Triflic anhydride and trimethylsi-
T.[10] The more reactive sugars, such as the deoxy derivat- lyl triflate, however, proved totally inefficient, while other
ives (-Fuc, -Rha), displayed higher tendencies to yield un- hard Lewis acids such as BF3·Et2O gave only poor glycosyl-
desired sulfoxide by-products.
ation yields, never exceeding 40%. In contrast, softer Lewis
Treatment of ethyl 2-acetamido-3,4,6-tri-O-acetyl-2-de- acids[14,15] such as cupric salts [Cu(OTf)2, for example]
oxy-1-thio-β--glucopyranoside[11] with chloramine T un- proved to be much more efficient promoters for the glycos-
der the standard reaction conditions furnished only the cor- ylation reaction (Scheme 4).
172
Eur. J. Org. Chem. 2002, 171Ϫ180

Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
FULL PAPER
Table 2. Sulfimides derived from diversely peracetylated thioglycos-
ides
Table 3. Reaction with the per-O-benzylated donor 4
[a]
1
[b]
α/β ratios were determined by H NMR. The yields in italics
correspond to rearranged products resulting from the 5,6Ǟ3,5 mi-
gration of an isopropylidene group.
Table 4. Reactions with the per-O-acetylated donor 1
[a]
1
de values were estimated by H NMR spectra.
[a]
1
[b]
α/β ratios were determined by H NMR. The yields in italics
correspond to rearranged products resulting from the 5,6Ǟ3,5 mi-
gration of an isopropylidene group.
Scheme 4
Et2O and in CH2Cl2, while CH3CN exhibited a β-orienting
effect.[16] A higher amount of β-linked glycoside was usually
Satisfactory glycosylation results were obtained only with obtained from donors with a participating group Ϫ such
excesses of glycosyl donor and promoter.[6] For example, 3 as an acetoxy moiety Ϫ at C(2), which often favoured the
equiv., based on 1 equiv. of glycosyl acceptor, of the benzyl- exclusive formation of a 1,2-trans-O-glycosidic orientation.
ated glucosyl donor 4 were used, together with 3.3 equiv. of Treatment of 1 with the same acceptors[6] as used above
Cu(OTf)2. Under these reaction conditions, short reaction selectively provided the β--linked glycosides 18 and 19
times (typically 5 min) were sufficient. In the case of per- (Table 4). In addition to 1, further pyranoid or furanoid
acetylated donors such as the -gluco derivative 1, the use peracetylated donors with different stereochemistries, such
of 2 equiv. of donor and 2.2 equiv. of Cu(OTf)2 (based on as 8, 13 and 15, have been investigated.
1 equiv. of acceptor) was appropriate, these conditions re-
Neighbouring participation by the 2-O-acetyl group also
quiring reactions times of ca. 5 h.
induced the exclusive formation of the 1,2-trans-O-glycos-
With these conditions established, the scope of the reac- idic linkage in these cases. In most cases the yields were
tion was explored by treatment of 4 with two acceptors of good, although moderate yields were obtained (for disac-
different reactivity (Table 3). For donors without a particip- charides 21Ϫ24, Scheme 5, for example) with acceptors of
ating group at C(2) the solvent may have a directing effect low reactivity or when the hydroxyl group of the glycosyl
on the stereochemistry at the anomeric centre, so the reac- acceptor was sterically hindered. In such cases though, the
tions with disaccharides 16 and 17 were studied in different glycosyl acceptor and/or the acetylated acceptor could be
solvents. As expected, an α-orienting effect was observed in recovered.
Eur. J. Org. Chem. 2002, 171Ϫ180
173

´
F. Chery, S. Cassel, H. P. Wessel, P. Rollin
FULL PAPER
Conclusion
In summary, we describe the preparation of anomeric sul-
fimides as a new family of carbohydrate-derived sulfur com-
pounds. Those sulfimides were easily prepared from the
corresponding thioglycosides by use of chloramine T, an
inexpensive and easily handled reagent.
Without the necessity of intermediate purification, anom-
eric sulfimides were successfully employed as glycosyl
donors. Compared to other glycosylation methods, the
yields and the stereoselectivity were similar, but the reaction
conditions were mild, reaction times were short Ϫ especially
for activated donors Ϫ and the promoter was easy to ma-
nipulate.
Experimental Section
General: Solvents were dried and distilled by standard methods. All
reagents were of commercial quality (Acros, Aldrich or Lancaster)
and were used without purification. Reactions were carried out un-
der dry argon and monitored by TLC analysis on silica gel plates
(Kieselgel 60 F254, Merck). Compounds were viewed under UV
light and by heat treatment with 10% sulfuric acid in ethanol. Col-
umn chromatography was performed on 60
M silica gel
(0.036Ϫ0.063 mm, Merck). 1H NMR (250 MHz) and 13C NMR
(62.59 MHz) spectra (CDCl3, TMS as internal standard) were re-
corded with a Bruker AVANCE DPX 250; for compound 6, 1H
NMR (500 MHz) and 13C NMR (125.7 MHz) spectra (CDCl3,
TMS as internal standard) were recorded with a Bruker AMX 500.
NMR simulations for 6 and 10 were produced with a Bruker pro-
gram (PANIC) fixing the chemical shift and with free coupling con-
stants. Chemical shifts (δ) are reported in ppm units by reference
to TMS; coupling constants (J) are reported in Hertz and refer to
apparent peak multiplicity. Assignments are based on H,H and
C,H COSY experiments. Mass spectra were obtained with an API
300 PerkinϪElmer SCIEX spectrometer, using the ionspray
method. HR-ESI-TOF-MS was carried out by Technologie Servier
Scheme 5
´
(Orleans, France). Optical rotations were measured in chloroform
at room temperature with a PerkinϪElmer 41 polarimeter.
General Procedure for the Synthesis of Sulfimides (Procedure A):
A dichloromethane solution of the thioglycoside was treated with
chloramine T (1.5 equiv.) and 1 drop of Aliquat 336 . The suspen-
sion was stirred at room temperature and after completion of the
reaction, the mixture was diluted with dichloromethane. The or-
ganic phase was washed with 5% aqueous NaOH, dried with
MgSO4 and filtered, and the solvents were evaporated under re-
duced pressure. The crude product could be purified by column
chromatography on silica gel to afford the pure sulfimide.
General Procedure for Glycosylation (Procedure B): The glycosyl
acceptor (1 equiv.) and CuO (1 equiv.) were added to a solution of
the dried crude perbenzylated sulfimide 4 (3 equiv.) in an anhyd-
rous solvent (Et2O, CH2Cl2 or CH3CN). The mixture was stirred
˚
with powdered molecular sieves (3 or 4 A, depending on the solv-
ent) for about 15 min in order to remove traces of water, and then
treated with Cu(OTf)2 (3.3 equiv.). The reaction mixture was stirred
until complete consumption of the starting material, 2 drops of
triethylamine were then added, and the mixture was stirred for an-
other 5 min and filtered through Celite . The filtrate was concen-
trated under reduced pressure and the crude product was chroma-
tographed on silica gel to afford the pure glycoside.
Scheme 6
174
Eur. J. Org. Chem. 2002, 171Ϫ180

Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
FULL PAPER
General Procedure for Glycosylation (Procedure C): The glycosyl
acceptor (1 equiv.) and CuO (1 equiv.) were added to a solution of
the dried crude peracetylated sulfimide (2.5 equiv.) in anhydrous
7.67 (d, 2 H, J ϭ 8.3, CH3Ar). 13C NMR (CDCl3): δ ϭ 8.1
(SCH2CH3), 21.8 (CH3Ar), 27.3, 27.4, 27.5 (CH3 Piv), 34.7
(SCH2CH3), 37.8, 37.9, 38.0 (C quat. Piv), 60.9 (C-6), 66.8 (C-4),
68.1 (C-2), 72.3 (C-3), 77.8 (C-5), 91.3 (C-1), 126.8, 129.6 (2 ϫ 2
˚
dichloromethane. The mixture was stirred with 4 A powered mo-
lecular sieves for about 15 min in order to remove traces of water, CH, CH3Ar), 139.9, 141.1 (2 C-arom. quat.), 175.2, 175.7, 176.6,
and then treated with Cu(OTf)2 (2 equiv.). The reaction mixture
was stirred until complete consumption of the starting material,
and 2 drops of triethylamine were then added. The mixture was
then stirred for another 5 min and filtered through Celite , and the
filtrate was concentrated under reduced pressure. The crude prod-
uct was chromatographed on silica gel to afford the pure glycoside.
176.8 (4 CO Piv). HRMS (C35H55NO11S2): calcd. 729.3214;
found 729.3211.
Ethyl 2,3,4,6-Tetra-O-benzoyl-S-(N-tosylimino)-1-thio-β-D-glucopy-
ranoside (3): Preparation from crystalline ethyl 2,3,4,6-tetra-O-
benzoyl-1-thio-β--glucopyranoside[19] (130 mg, 0.202 mmol) ac-
cording to Procedure A and purification by column chromato-
graphy (petroleum ether/ethyl acetate, 6:4) gave amorphous 3 (149
mg, yield 91%) in the form ofone epimer. [α]D ϭ Ϫ123 (c ϭ 1.0,
CHCl3). 1H NMR (CDCl3): δ ϭ 1.21 (t, Jvic ϭ 7.5 Hz, 3 H,
SCH2CH3), 2.31 (s, 3 H, CH3Ar), 3.12 (dq, 1 H, Jgem ϭ Ϫ12.8,
SCH2CH3), 3.28 (dq, 1 H, SCH2CH3), 4.30 (m, 1 H, H-5), 4.48
Ethyl 2,3,4,6-Tetra-O-acetyl-S-(N-tosylimino)-1-thio-β-D-glucopyr-
anoside (1): Preparation from crystalline ethyl 2,3,4,6-tetra-O-acetyl-
1-thio-β--glucopyranoside[17] (250 mg, 0.637 mmol) according to
Procedure A and purification by column chromatography (petro-
leum ether/ethyl acetate, 2:8) gave amorphous 1 (307 mg, yield 86%)
in the form of one epimer. [α]D ϭ Ϫ166 (c ϭ 1.0; CHCl3). 1H NMR
(CDCl3): δ ϭ 1.13 (t, Jvic ϭ 7.8 Hz, 3 H, SCH2CH3), 1.99, 2.01,
2.06, 2.11 (4 s, 12 H, 4 COCH3), 2.38 (s, 3 H, CH3Ar), 2.93 (dq, 1
H, Jgem ϭ Ϫ13.5, SCH2CH3), 3.16 (dq, 1 H, SCH2CH3), 3.83 (ddd,1
H, J5,6a ϭ 4.6, H-5), 4.14 (dd, 1 H, J5,6b ϭ 2.2, H-6b), 4.30 (dd, 1
H, J6a,6b ϭ Ϫ12.7, H-6a), 4.59 (d 1 H, J1,2 ϭ 10.0 Hz, H-1), 4.98 (t,
1 H, J2,3 ϭ 10.0 Hz, H-2), 5.02 (t, 1 H, J3,4 ϭ J4,5 ϭ 10.0 Hz, H-4),
5.24 (t, 1 H, H-3),7.22 (d, Jvic ϭ 8.1 Hz, 2 H, CH3Ar), 7.76 (d, Jvic ϭ
8.1 Hz, 2 H, CH3Ar). 13C NMR (CDCl3): δ ϭ 7.8 (SCH2CH3), 20.8,
20.9, 21.1 (4 COCH3), 21.9 (CH3Ar), 36.4 (SCH2CH3), 61.5 (C-6),
67.1 (C-4),68.0 (C-2), 74.1 (C-3), 76.6 (C-5), 90.5 (C-1), 126.3, 129.6
(2 ϫ 2 CH, CH3Ar), 139.2, 142.0 (2 C-arom. quat.), 169.3, 169.6,
170.0, 170.4 (4 COCH3). HRMS (C23H31NO11S2): calcd. 561.1337;
found 561.1344.
(dd, 1 H, J5,6b ϭ 4.2, H-6b), 4.76 (dd, 1 H, J5,6a ϭ 2.9, J6a,6b
ϭ
Ϫ12.8, H-6a), 4.97 (d 1 H, J1,2 ϭ 9.8 Hz, H-1), 5.40 (t, J2,3 ϭ 9.8
Hz, 1 H, H-2), 5.68 (‘‘t’’, 1 H, J3,4 ϭ 9.8, J4,5 ϭ 9.8 Hz, H-4), 5.95
(t, 1 H, H-3), 6.99 (d, Jvic ϭ 8.1 Hz, 2 H, CH3Ar), 7.24Ϫ7.59 (m,
14 H, Bz, CH3Ar), 7.80Ϫ7.87 (m, 4 H, Bz), 7.96Ϫ8.04 (m, 4 H,
Bz). 13C NMR (CDCl3): δ ϭ 8.1 (SCH2CH3), 21.8 (CH3Ar), 36.3
(SCH2CH3), 62.5 (C-6), 68.5 (C-4), 68.8 (C-2), 73.1 (C-3), 77.8 (C-
5), 91.1 (C-1), 126.3Ϫ142.3 (24 CH, 6 C-arom. quat., 4Bz, CH3Ar),
165.4, 165.7, 166.1, 166.3 (4 CO Bz). HRMS (C43H39NO11S2):
calcd. 809.1963; found 809.1972.
Ethyl 2,3,4,6-Tetra-O-benzyl-S-(N-tosylimino)-1-thio-β-D-glucopyr-
anoside (4): Preparation from crystalline ethyl 2,3,4,6-tetra-O-
benzyl-1-thio-β--glucopyranoside[18] (342 mg, 0.585 mmol) ac-
cording to Procedure A and purification by column chromato-
graphy (petroleum ether/ethyl acetate, 6:4) gave amorphous 4 (384
mg, yield 87%) as a 4:1 mixture of diastereomers. [α]D ϭ Ϫ31 (c ϭ
Ethyl 2,3,4,6-Tetra-O-pivaloyl-S-(N-tosylimino)-1-thio-β-D-glucopy-
ranoside (2): A solution of ethyl 1-thio-β--glucopyranoside[18] (2
g, 8.9 mmol) in pyridine (10 mL) was treated with pivaloyl chloride
(8 equiv.); an exothermic reaction occurred, with formation of a
precipitate. After 6 h, DMAP (0.1 equiv.) was added to activate the
reaction and stirring was maintained overnight. Standard workup
involved treatment with methanol (6 equiv.) at 0 °C, dilution in
dichloromethane, washing with water and drying with MgSO4; the
crude solid obtained after evaporation of the solvents and coevap-
oration with toluene was crystallised from 2-propanol/water to af-
ford ethyl 2,3,4,6-tetra-O-pivaloyl-1-thio-β--glucopyranoside (2.1
g, yield 42%). Colourless crystals, [α]D ϭ Ϫ14 (c ϭ 1.6; CHCl3),
1
1.0, CHCl3). H NMR (CDCl3) for the major epimer: δ ϭ 1.07 (t,
Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 2.36 (s, 3 H, CH3Ar), 2.36 (dq, 1
H, Jgem ϭ Ϫ12.8, SCH2CH3), 2.71 (dq, 1 H, SCH2CH3), 3.63Ϫ4.02
(m, 6 H, H-2, H-3, H-4, H-5, H-6a, H-6b), 4.47Ϫ4.97 (m, 9 H, 1-
H, 4 CH2Ph), 7.17 (d, Jvic ϭ 7.9 Hz, 2 H, CH3Ar), 7.23Ϫ7.39 (m,
20 H, 4 CH2Ph), 7.83 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar); for the minor
epimer: δ ϭ 1.12 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 2.38 (s, 3 H,
CH3Ar), 2.86 (dq, 1 H, Jgem ϭ Ϫ14.8, SCH2CH3), 3.20 (dq, 1 H,
SCH2CH3), 3.58Ϫ4.20 (m, 6 H, H-2, H-3, H-4, H-5, H-6a, H-6b),
4.34Ϫ4.96 (m, 9 H, 1-H, 4 CH2Ph), 7.19 (d, 2 H, J ϭ 7.9, CH3Ar),
7.27Ϫ7.35 (m, 20 H, 4 CH2Ph), 7.85 (d, Jvic ϭ 8.1 Hz, 2 H,
CH3Ar). 13C NMR (CDCl3) for the major epimer: δ ϭ 7.9
(SCH2CH3), 21.9 (CH3Ar), 38.6 (SCH2CH3), 68.7 (C-6), 75.9, 76.0,
76.7, 76.8 (4 CH2Ph), 77.3, 78.8, 80.5, 86.4 (C-2, C-3, C-4, C-5),
92.8 (C-1), 127.0Ϫ130.0 (24 CH, 4 CH2Ph, CH3Ar), 141.9, 142.0
(2 C-arom. quat., CH3Ar), 137.4, 138.1, 138.2, 138.3 (4 C-arom.
quat., 4 CH2Ph); for the minor epimer: δ ϭ 7.8 (SCH2CH3), 21.8
(CH3Ar), 39.9 (SCH2CH3), 69.1 (C-6), 73.8, 75.5, 75.6, 76.9 (4
CH2Ph), 77.4, 77.9, 80.5, 80.8 (C-2, C-3, C-4, C-5), 88.9 (C-1),
126.4Ϫ129.5 (24 CH, 4 CH2Ph, CH3Ar), 137.8Ϫ142.1 (6 C-arom.
quat, 4 CH2Ph, CH3Ar). HRMS (C43H47NO7S2): calcd. 753.2792;
found 753.2801.
1
m.p. 128Ϫ130 °C. H NMR (CDCl3): δ ϭ 1.11, 1.14, 1.16, 1.21 (4
s, 36 H, Piv), 1.26 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 2.28Ϫ2.56
(m, 2 H, SCH2CH3), 3.73 (ddd, 1 H, H-5), 4.05 (d, 1 H, J5,6b
ϭ
5.3, H-6b), 4.21 (d, 1 H, J5,6a ϭ 1.5, J6a,6b ϭ Ϫ12.3, H-6a), 4.51 (d
1 H, J1,2 ϭ 10.0 Hz, H-1), 5.06, 5.11 (2t, 2 H, H-2, H-4), 5.33 (t,
J3,4 ϭ 9.3 Hz, 1 H, J2,3 ϭ 9.3, H-3). 13C NMR (CDCl3): δ ϭ 15.3
(SCH2CH3), 24.2 (SCH2CH3), 27.4, 27.5, 27.6 (CH3 Piv), 39.0,
39.1, 39.2 (C quat. Piv), 62.5 (C-6), 68.2 (C-5), 69.9, 73.6 (C-2, C-
4), 76.8 (C-3), 83.8 (C-1), 176.8, 176.9, 177.5, 178.4 (4 CO Piv).
HRMS (C28H48O9S): calcd. 560.3016; found 560.3021. Treatment
of the above thioglucosidic precursor (170 mg, 0.303 mmol) accord-
ing to Procedure A and purification by column chromatography
(petroleum ether/ethyl acetate, 7:3) gave amorphous 2 (184 mg,
yield 83%) in the form of one epimer. [α]D ϭ Ϫ135 (c ϭ 1.23,
Ethyl 2,3-Di-O-acetyl-4,6-O-benzylidene-S-(N-tosylimino)-1-thio-β-
D-glucopyranoside (5): Preparation from crystalline ethyl 2,3-di-O-
CHCl3). 1H NMR (CDCl3): δ ϭ 1.06Ϫ1.17 (m, 39 H, Piv, acetyl-4,6-O-benzylidene-1-thio-β--glucopyranoside[20] (97 mg,
SCH2CH3), 2.34 (s, 3 H, CH3Ar), 2.91 (dq, 1 H, Jgem ϭ Ϫ13.4, 0.244 mmol) according to Procedure A and purification by column
SCH2CH3), 3.19 (dq, 1 H, SCH2CH3), 3.84 (dt, 1 H, J5,6a ϭ J5,6b ϭ
chromatography (petroleum ether/ethyl acetate, 3:7) gave amorph-
2.8, H-5), 4.18 (d, 2 H, H-6a, H-6b), 4.57 (d 1 H, J1,2 ϭ 10.2 Hz, ous 5 (127 mg, yield: 92%) in the form of one epimer. [α]D ϭ Ϫ177
1
H-1), 4.84 (t, 1 H, J2,3 ϭ 10.2 Hz, H-2), 5.11 (t, 1 H, J3,4 ϭ J4,5
ϭ
(c ϭ 1.0, CHCl3). H NMR (CDCl3): δ ϭ 1.13 (t, Jvic ϭ 7.4 Hz, 3
10.2 Hz, H-4), 5.35 (t, 1 H, H-3), 7.17 (d, 2 H, J ϭ 8.3, CH3Ar), H, SCH2CH3), 2.02, 2.07 (2 s, 6 H, 2 COCH3), 2.37 (s, 3 H,
Eur. J. Org. Chem. 2002, 171Ϫ180
175

´
F. Chery, S. Cassel, H. P. Wessel, P. Rollin
FULL PAPER
CH3Ar), 2.93 (dq, 1 H, Jgem ϭ Ϫ14.2, SCH2CH3), 3.10 (dq, 1 H, (dd, 1 H, J2,3 ϭ 3.4 Hz, H-2), 7.25 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar),
SCH2CH3), 3.55Ϫ3.71 (m, 3 H, H-4, H-5, H-6b), 4.38 (dd, 1 H, 7.82 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar); for the minor epimer: δ ϭ
J5,6a ϭ 2.7, J6a,6b ϭ Ϫ9.4, H-6a), 4.59 (d 1 H, J1,2 ϭ 10.1 Hz, H- 1.22 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 2.02, 2.06, 2.07, 2.09 (4 s,
1), 5.00 (t, 1 H, J2,3 ϭ 10.1 Hz, H-2), 5. 33 (t, 1 H, J3,4 ϭ 10.1 Hz, 12 H, 4 COCH3), 2.30 (s, 3 H, CH3Ar), 2.92Ϫ3.12 (m, 2 H,
H-3), 5.43 (s, 1 H, H-7), 7.22 (d, Jvic ϭ 8.1 Hz, 2 H, CH3Ar), SCH2CH3), 4.09 (dd, 1 H, J5,6b ϭ 2.7, H-6b), 4.28 (dd, 1 H, J5,6a ϭ
7.32Ϫ7.41 (m, 5 H, Ph), 7.74 (d, Jvic ϭ 8.1 Hz, 2 H, CH3Ar). 13C
5.2, J6a,6b ϭ Ϫ12.6, H-6a), 4.42Ϫ4.45 (m, 1 H, H-5), 4.91 (d, J1,2 ϭ
NMR (CDCl3): δ ϭ 8.0 (SCH2CH3), 21.9, 21.8, 21.4 (2 COCH3, 3.2 Hz, 1 H, H-1), 5.23 (t, 1 H, J4,5 ϭ 10.5 Hz, H-4), 5.38 (dd, 1
CH3Ar), 36.7 (SCH2CH3), 65.2 (C-6), 68.2 (C-2), 71.7, 77.9 (C-4, H, J3,4 ϭ 10.5 Hz, H-3), 5.59 (dd, 1 H, J2,3 ϭ 3.4 Hz, H-2), 7.24
C-5), 72.6 (C-3), 92.4 (C-1), 102.1 (C-7), 126.5Ϫ129.9 (9 CH, Ph,
(d, Jvic ϭ 8.2 Hz, 2 H, CH3Ar), 7.81 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar).
CH3Ar), 130.1, 141.4, 142.5 (3 C-arom. quat.), 169.9, 170.1 (2 13C NMR (CDCl3) for the major epimer: δ ϭ 6.3 (SCH2CH3),
COCH3). HRMS (C26H31NO9S2): calcd. 565.1439; found 565.1441.
Ethyl 2,3,4-Tri-O-acetyl-S-(N-tosylimino)-1-thio-α- -xylopyrano-
20.1Ϫ21.2 (4 COCH3), 20.3 (CH3Ar), 40.9 (SCH2CH3), 62.4 (C-
6), 65.7 (C-5), 66.1 (C-4), 67.5 (C-3), 71.3 (C-2), 91.0 (C-1),
126.0Ϫ129.3 (4 CH, CH3Ar), 141.7, 141.8 (2 C-arom. quat.,
CH3Ar), 168.4Ϫ170.3 (4 COCH3); for the minor epimer: δ ϭ 7.5
(SCH2CH3), 20.1Ϫ21.2 (4 COCH3), 22.1 (CH3Ar), 39.5
(SCH2CH3), 61.7 (C-6), 65.9 (C-5), 66.3 (C-4), 68.7 (C-3), 69.4 (C-
2), 89.2 (C-1), 127.4Ϫ129.3 (4 CH, CH3Ar), 140.7, 141.8 (2 C-
arom. quat, CH3Ar), 168.4Ϫ170.3 (4 COCH3). HRMS
(C23H31NO11S2): calcd. 561.1337; found 561.1333.
D
side (6): Preparation from syrupy ethyl 2,3,4-tri-O-acetyl-1-thio-α-
-xylopyranoside[21] (136 mg, 0.425 mmol) according to Procedure
A and purification by column chromatography (petroleum ether/
ethyl acetate, 2:8) gave amorphous 6 (196 mg, yield 94%) in the
form of one epimer. [α]D ϭ Ϫ70 (c ϭ 1.0, CHCl3). 1H NMR
(CDCl3): δ ϭ 1.16 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 2.02, 2.05
2.10 (3 s, 9 H, 3 COCH3), 2.34 (s, 3 H, CH3Ar), 2.91 (dq, 1 H,
Jgem ϭ Ϫ14.3, SCH2CH3), 3.08 (dq, 1 H, SCH2CH3), 3.93 (dd, 1
H, J4,5a ϭ 1.8, H-5a), 4.16 (ddd, 1 H, J3,5b ϭ 1.7, J4,5b ϭ 2.1,
J5a,5b ϭ Ϫ13.3, H-5b), 4.74 (m, 1 H, H-4), 4.84 (d, J1,2 ϭ 1.8 Hz,
1 H, H-1), 5.03 (ddd, 1 H, J2,3 ϭ 2.8, J2,4 ϭ 1.2 Hz, H-2), 5.35
(ddd, 1 H, J3,4 ϭ 3.1 Hz, H-3), 7.19 (d, Jvic ϭ 8.1 Hz, 2 H, CH3Ar),
7.69 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar). 13C NMR (CDCl3): δ ϭ 6.5
(SCH2CH3), 20.4, 20.7, 20.8 (3 COCH3), 21.4 (CH3Ar), 40.1
(SCH2CH3), 64.4 (C-2), 65.0 (C-3), 65.8 (C-4), 68.1 (C-5), 88.8 (C-
1), 126.3, 129.3 (2 ϫ 2 CH, CH3Ar), 140.7, 142.0 (2 C-arom. quat.,
CH3Ar), 168.1, 168.8, 169.4 (3 COCH3). HRMS (C20H27NO9S2):
calcd. 489.1126; found 489.1120.
Ethyl 2,3,4,6-Tetra-O-acetyl-S-(N-tosylimino)-1-thio-β-D-mannopyr-
anoside (9): Ethyl 2,3,4,6-tetra-O-acetyl-1-thio-β--mannopyrano-
side was obtained as a syrupy by-product in the synthesis of its α-
1
counterpart.[21] [α]D ϭ ϩ37 (c ϭ 1.1, CHCl3). H NMR (CDCl3):
δ ϭ 1.23 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 1.90, 1.97, 2.00, 2.11
(4 s, 12 H, 4 COCH3), 2.67 (bd, 2 H, SCH2CH3), 3.65 (ddd, 1 H,
H-5), 4.06 (dd, 1 H, J5,6b ϭ 2.5, H-6b), 4.20 (dd, 1 H, J5,6a ϭ 5.9,
J6a,6b ϭ 12.2, H-6a), 4.74 (d 1 H, J1,2 ϭ 1.0 Hz, H-1), 5.01 (dd, 1
H, J3,4 ϭ 10.1 Hz, H-3), 5.18 (dd, 1 H, J4,5 ϭ 10.1 Hz, H-4), 5.43
(dd, 1 H, J2,3 ϭ 3.4 Hz, H-2). 13C NMR (CDCl3): δ ϭ 15.3
(SCH2CH3), 20.5Ϫ20.8 (4 COCH3), 26.2 (SCH2CH3), 62.8 (C-6),
63.1 (C-4), 70.5 (C-2), 71.9 (C-3), 76.4 (C-5), 82.9 (C-1),
169.6Ϫ170.6 (4 COCH3). Preparation from ethyl 2,3,4,6-tetra-O-
acetyl-1-thio-β--mannopyranoside (80 mg, 0.203 mmol) according
to Procedure A and purification by column chromatography (pet-
roleum ether/ethyl acetate, 2:8) gave amorphous 9 (80 mg, yield
70%) as a 4:1 mixture of diastereomers. [α]D ϭ Ϫ18 (c ϭ 1.0,
CHCl3). 1H NMR (CDCl3) for the major epimer: δ ϭ 1.22 (t, Jvic ϭ
7.4 Hz, 3 H, SCH2CH3), 1.96, 2.04, 2.06, 2.08 (4 s, 12 H, 4
COCH3), 2.37 (s, 3 H, CH3Ar), 3.05Ϫ3.15 (m, 2 H, SCH2CH3),
3.87 (ddd, 1 H, H-5), 4.15 (dd, 1 H, J5,6b ϭ 2.6, H-6b), 4.22 (dd, 1
H, J5,6a ϭ 5.3, J6a,6b ϭ Ϫ12.5, H-6a), 4.94 (d 1 H, J1,2 ϭ 1.1 Hz,
Ethyl 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-S-(N-tosylimino)-1-
thio-β-D-glucopyranoside (7): Preparation from ethyl 3,4,6-tri-O-
acetyl-2-deoxy-2-phthalimido-1-thio-β--glucopyranoside[22] (160
mg, 0.334 mmol) according to Procedure A and purification by
column chromatography (petroleum ether/ethyl acetate, 2:8) gave
amorphous 7 (141 mg, yield 65%) in the form of one epimer. [α]D ϭ
1
Ϫ46 (c ϭ 1.0, CHCl3). H NMR (CDCl3): δ ϭ 1.11 (t, Jvic ϭ 7.3
Hz, 3 H, SCH2CH3), 1.82, 2.00, 2.07 (3 s, 9 H, 3 COCH3), 2.32 (s,
3 H, CH3Ar), 2.92 (dq, 1 H, Jgem ϭ Ϫ13.5, SCH2CH3), 3.07 (dq,
1 H, SCH2CH3), 3.94 (ddd, 1 H, J5,6a ϭ 4.6, H-5), 4.18 (dd, 1 H,
J5,6b ϭ 1.9, H-6b), 4.30 (dd, 1 H, J6a,6b ϭ Ϫ12.7, H-6a), 4.51 (dd,
1 H, J2,3 ϭ 10.1 Hz, H-2), 5.09 (dd, 1 H, J3,4 ϭ 9.5, J4,5 ϭ 10.3
Hz, H-4), 5.45 (d 1 H, J1,2 ϭ 10.8 Hz, H-1), 5.83 (dd, 1 H, H-3),
7.06 (d, Jvic ϭ 8.5 Hz, 2 H, CH3Ar), 7.48 (d, Jvic ϭ 8.3 Hz, 2 H,
CH3Ar), 7.71Ϫ7.85 (m, 4 H, Phth). 13C NMR (CDCl3): δ ϭ 7.2
(SCH2CH3), 20.4Ϫ21.5 (3 COCH3), 21.6 (CH3Ar), 37.8
(SCH2CH3), 61.4 (C-6), 67.8 (C-4), 70.7 (C-3), 74.7 (C-2), 77.7 (C-
5), 87.3 (C-1), 123.8Ϫ134.7 (8 CH, CH3Ar), 141.2Ϫ142.2 (4 C-
arom. quat., Phth, CH3Ar), 167.7Ϫ170.9 (2 CO-Phth, 3 COCH3).).
HRMS (C29H32N2O11S2): calcd. 648.1447; found 648.1432.
H-1), 5.12 (dd, 1 H, J3,4 ϭ 10.1 Hz, H-3), 5.23 (dd, 1 H, J4,5
10.3 Hz, H-4), 5.74 (dd, 1 H, J2,3 ϭ 3.2 Hz, H-2), 7.21 (d, Jvic
ϭ
ϭ
7.9 Hz, 2 H, CH3Ar), 7.71 (d, Jvic ϭ 8.2 Hz, 2 H, CH3Ar); for the
minor epimer: δ ϭ 1.22 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3), 2.03,
2.04, 2.08 (3 s, 12 H, 4 COCH3), 2.38 (s, 3 H, CH3Ar), 3.03Ϫ3.15
(m, 2 H, SCH2CH3), 4.06Ϫ4.39 (m, 3 H, H-5, H-6a, H-6b), 4.92
(d, J1,2 ϭ 1.0 Hz, 1 H, H-1), 5.16Ϫ5.28 (m, 2 H, H-3, H-4), 5.67
(dd, 1 H, J2,3 ϭ 3.8 Hz, H-2), 7.24 (d, Jvic ϭ 7.7 Hz, 2 H, CH3Ar),
7.76 (d, Jvic ϭ 8.2 Hz, 2 H, CH3Ar). 13C NMR (CDCl3) for the
major epimer: δ ϭ 7.1 (SCH2CH3), 20.9Ϫ21.8 (4 COCH3), 22.0
(CH3Ar), 41.0 (SCH2CH3), 62.9 (C-6), 65.7 (C-4), 66.5 (C-3), 71.4
(C-2), 77.9 (C-5), 90.1 (C-1), 126.3Ϫ129.7 (4 CH, CH3Ar), 141.0,
143.0 (2 C-arom. quat., CH3Ar), 169.8Ϫ171.3 (4 COCH3); for the
minor epimer: δ ϭ 7.2 (SCH2CH3), 20.9Ϫ21.8 (4 COCH3), 22.2
(CH3Ar), 42.1 (SCH2CH3), 61.3 (C-6), 65.3 (C-4), 66.3 (C-3), 71.4
(C-2), 78.1 (C-5), 89.5 (C-1), 126.3Ϫ129.7 (4 CH, CH3Ar), 141.0,
143.0 (2 C-arom. quat., CH3Ar), 169.8Ϫ171.3 (4 COCH3). HRMS
(C23H31NO11S2): calcd. 561.1337; found 561.1339.
Ethyl 2,3,4,6-Tetra-O-acetyl-S-(N-tosylimino)-1-thio-α-D-mannopy-
ranoside (8): Preparation from ethyl 2,3,4,6-tetra-O-acetyl-1-thio-α-
-mannopyranoside[21] (184 mg, 0.469 mmol) according to Proced-
ure A and purification by column chromatography (petroleum
ether/ethyl acetate, 2:8) gave amorphous 8 (184 mg, yield 70%) as
1
a 5:1 mixture of diastereomers. [α]D ϭ ϩ63 (c ϭ 1.0, CHCl3). H
NMR (CDCl3) for the major epimer: δ ϭ 1.35 (t, Jvic ϭ 7.3 Hz, 3
H, SCH2CH3), 1.99, 2.05, 2.08, 2.13 (4 s, 12 H, 4 COCH3), 2.39 (s,
3 H, CH3Ar), 2.92Ϫ3.12 (m, 2 H, SCH2CH3), 3.88 (ddd, 1 H,
J5,6a ϭ 5.8, H-5), 4.09 (dd, 1 H, J5,6b ϭ 2.7, H-6b), 4.23 (dd, 1 H, Ethyl 2,3,4,6-Tetra-O-acetyl-S-(N-tosylimino)-1-thio-α-D-galactopy-
J6a,6b ϭ Ϫ12.5, H-6a), 4.98 (d, J1,2 ϭ 2.2 Hz, 1 H, H-1), 5.20 (t, ranoside (10): Preparation from syrupy ethyl 2,3,4,6-tetra-O-acetyl-
J4,5 ϭ 9.3 Hz, 1 H, H-4), 5.37 (dd, 1 H, J3,4 ϭ 9.3 Hz, H-3), 5.59 1-thio-α--galactopyranoside[21] (73 mg, 0.186 mmol) according to
176
Eur. J. Org. Chem. 2002, 171Ϫ180

Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
FULL PAPER
Procedure A and purification by column chromatography (petro-
leum ether/ethyl acetate, 2:8) gave amorphous 10 (91 mg, yield
87%) as a 4:1 mixture of diastereomers. [α]2D0 ϭ ϩ97 (c ϭ 1.0,
Ethyl
2,3,4-Tri-O-acetyl-S-(N-tosylimino)-1-thio-α-
L-rhamnopyr-
anoside (13): Preparation from syrupy ethyl 2,3,4-tri-O-acetyl-1-
thio-α--rhamnopyranoside[24] (230 mg, 0.688 mmol) according to
CHCl3). 1H NMR (CDCl3) for the major epimer: δ ϭ 1.12 (t, Jvic ϭ Procedure A and purification by column chromatography (petro-
7.3 Hz, 3 H, SCH2CH3), 2.04, 2.06, 2.13, 2.18 (4 s, 12 H, 4 leum ether/ethyl acetate, 2:8) gave amorphous 13 (242 mg, yield:
COCH3), 2.38 (s, 3 H, CH3Ar), 2.81Ϫ2.90 (m, 2 H, SCH2CH3), 70%) as a 3:1 mixture of diastereomers. [α]D ϭ Ϫ76 (c ϭ 1.0,
4.02 (dd, 1 H, J5,6b ϭ 3.9, H-6b), 4.14Ϫ4.18 (m, 1 H, H-5), 4.29 CHCl3). 1H NMR (CDCl3) for the major epimer: δ ϭ 1.22 (d,
(dd, 1 H, J5,6a ϭ 7.8, J6a,6b ϭ Ϫ11.5, H-6a), 5.32Ϫ5.35 (m, 1 H, Jvic ϭ 6.1 Hz, 3 H, CH3), 1.38 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3),
H-1), 5.51Ϫ5.54 (m, 2 H, H-2, H-3), 5.55Ϫ5.59 (m, 1 H, H-4), 7.24 1.95, 2.04, 2.12 (3 s, 9 H, 3 COCH3), 2.34 (s, 3 H, CH3Ar),
(d, Jvic ϭ 8.5 Hz, 2 H, CH3Ar), 7.76 (d, Jvic ϭ 8.1 Hz, 2 H, CH3Ar),
for the minor epimer: δ ϭ 1.26 (t, Jvic ϭ 7.2 Hz, 3 H, SCH2CH3), 1.7 Hz, 1 H, H-1), 5.00 (t, 1 H, J4,5 ϭ 9.5, H-4), 5.25 (d 1 H, J3,4 ϭ
2.04, 2.07, 2.13, 2.18 (4 s, 12 H, 4 COCH3), 2.37 (s, 3 H, CH3Ar), 9.5 Hz, H-3), 5.52 (dd, 1 H, J2,3 ϭ 3.6 Hz, H-2), 7.23 (d, Jvic ϭ 8.2
3.03 (dq, 1 H, Jgem ϭ 13.5 Hz, SCH2CH3), 3.20 (dq, 1 H, Hz, 2 H, CH3Ar), 7.80 (d, Jvic ϭ 8.2 Hz, 2 H, CH3Ar); for the
SCH2CH3), 4.04Ϫ4.19 (m, 3 H, H-5, H-6a, H-6b), 5.33 (d, J1,2 minor epimer: δ ϭ 1.22 (d, Jvic ϭ 6.5 Hz, 3 H, CH3); 1.38 (t, Jvic ϭ
3.4 Hz, 1 H, H-1), 5.56Ϫ5.59 (m, 2 H, H-2, H-4), 5.79 (dd, 1 H, 6.5 Hz, 3 H, SCH2CH3), 1.97, 2.05, 2.13 (3 s, 9 H, 3 COCH3), 2.36
J2,3 ϭ 10.7, J3,4 ϭ 3.2 Hz, H-3), 7.24 (d, Jvic ϭ 8.5 Hz, 2 H, (s, 3 H, CH3Ar), 2.85Ϫ3.07 (m, 2 H, SCH2CH3), 3.92 (dq, 1 H, H-
2.85Ϫ3.07 (m, 2 H, SCH2CH3), 3.72 (dq, 1 H, H-5), 4.91 (d, J1,2 ϭ
ϭ
CH3Ar), 7.82 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar). 13C NMR (CDCl3) 5), 4.36 (d, J1,2 ϭ 2.1 Hz, 1 H, H-1), 5.02 (t, 1 H, J4,5 ϭ 9.5, H-4),
for the major epimer: δ ϭ 6.4 (SCH2CH3), 20.9Ϫ21.8 (4 COCH3), 5.21 (d 1 H, J3,4 ϭ 9.5 Hz, H-3), 5.65 (dd, 1 H, J2,3 ϭ 3.5 Hz, H-
22.5 (CH3Ar), 40.1 (SCH2CH3), 61.3 (C-6), 66.6, 66.7, 67.6, 74.1 2), 7.21 (d, Jvic ϭ 7.8 Hz, 2 H, CH3Ar), 7.78 (d, Jvic ϭ 8.8 Hz,
(C-2, C-3, C-4, C-5), 87.6 (C-1), 126.6Ϫ129.7 (4 CH, CH3Ar), 2 H, CH3Ar). 13C NMR (CDCl3) for the major epimer: δ ϭ 7.1
141.8Ϫ142.3 (2 C-arom. quat., CH3Ar), 169.6Ϫ170.7 (4 COCH3); (SCH2CH3), 17.9 (CH3), 20.7Ϫ21.8 (3 COCH3), 21.9 (CH3Ar),
for the minor epimer: δ ϭ 8.5 (SCH2CH3), 20.9Ϫ21.8 (4 COCH3),
40.9 (SCH2CH3), 66.6 (C-2), 68.2 (C-3), 70.6 (C-4), 73.5 (C-5), 91.5
22.2 (CH3Ar), 39.9 (SCH2CH3), 61.0 (C-6), 61.3Ϫ74.1 (C-2, C-3, (C-1), 126.2Ϫ129.9 (4 CH, CH3Ar), 135.8, 139.9 (2 C-arom. quat.,
C-4, C-5), 86.6 (C-1), 126.6Ϫ129.7 (4 CH, CH3Ar), 141.8Ϫ142.3 CH3Ar), 169.0Ϫ169.7 (3 COCH3); for the minor epimer: δ ϭ 7.0
(2 C-arom. quat., CH3Ar), 169.6Ϫ170.7 (4 COCH3). HRMS
(C23H31NO11S2): calcd. 561.1337; found 561.1328.
(SCH2CH3), 17.8 (CH3), 20.0Ϫ21.9 (3 COCH3), 21.8 (CH3Ar),
34.3 (SCH2CH3), 66.6 (C-2), 69.3 (C-3), 71.6 (C-4), 75.4 (C-5), 90.7
(C-1), 126.2Ϫ129.9 (4 CH, CH3Ar), 141.4, 143.5 (2 C-arom. quat.,
CH3Ar), 168.3Ϫ169.7 (3 COCH3). HRMS (C21H29NO9S2): calcd.
503.1283; found 503.1269.
Ethyl 2,3,4,6-Tetra-O-acetyl-S-(N-tosylimino)-1-thio-β-D-galactopy-
ranoside (11): Preparation from syrupy ethyl 2,3,4,6-tetra-O-acetyl-
1-thio-β--galactopyranoside[17] (140 mg, 0.357 mmol) according
to Procedure A and purification by column chromatography (petro-
leum ether/ethyl acetate, 2:8) gave amorphous 11 (130 mg, yield
65%) in the form of one epimer. [α]D ϭ Ϫ122 (c ϭ 1.0, CHCl3).
1H NMR (CDCl3): δ ϭ 1.13 (t, Jvic ϭ 7.4 Hz, 3 H, SCH2CH3),
1.95, 2.02, 2.10, 2.12 (4 s, 12 H, 4 COCH3), 2.36 (s, 3 H, CH3Ar),
2.92 (dq, 1 H, Jgem ϭ Ϫ13.5, SCH2CH3), 3.15 (dq, 1 H, SCH2CH3),
4.05Ϫ4.18 (m, 3 H, H-5, H-6a, H-6b), 4.56 (d 1 H, J1,2 ϭ 9.9 Hz,
H-1), 5.08 (dd, 1 H, J3,4 ϭ 3.1 Hz, H-3), 5.13 (t, J2,3 ϭ 9.9 Hz, 1
H, H-2), 5.43 (d, 1 H, J4,5 Ͻ 0.5, H-4), 7.21 (d, Jvic ϭ 8.2 Hz, 2 H,
CH3Ar), 7.71 (d, Jvic ϭ 8.2 Hz, 2 H, CH3Ar). 13C NMR (CDCl3):
δ ϭ 9.5 (SCH2CH3), 20.8, 20.9, 21.0 (4 COCH3), 23.5 (CH3Ar),
37.7 (SCH2CH3), 61.7 (C-6), 67.3 (C-3), 68.8 (C-4), 72.9 (C-2), 78.1
(C-5), 93.1 (C-1), 126.3, 129.9 (2 ϫ 2 CH, CH3Ar), 144.1, 142.9 (2
C-arom. quat., CH3Ar), 171.3, 171.8, 172.4, 172.5 (4 COCH3).
HRMS (C23H31NO11S2): calcd. 561.1337; found 561.1335.
Ethyl
2,3,4-Tri-O-acetyl-S-(N-tosylimino)-1-thio-β-L-rhamnopyr-
anoside (14): Preparation from syrupy ethyl 2,3,4-tri-O-acetyl-1-
thio-β--rhamnopyranoside[24] (112 mg, 0.335 mmol) according to
Procedure A and purification by column chromatography (petro-
leum ether/ethyl acetate, 2:8) gave amorphous 14 (118 mg, yield
70%) in the form of one epimer. [α]D ϭ ϩ97 (c ϭ 1.0, CHCl3). H
NMR (CDCl3): δ ϭ 1.23 (d, Jvic ϭ 6.1 Hz, 3 H, CH3), 1.27 (t,
1
Jvic ϭ 7.3 Hz, 3 H, SCH2CH3), 1.98, 2.06, 2.09 (3 s, 9 H, 3 COCH3),
2.38 (s, 3 H, CH3Ar), 2.99Ϫ3.15 (m, 2 H, SCH2CH3), 3.68 (dq, 1
H, H-5), 4.81 (d, J1,2 ϭ 1.2 Hz, 1 H, H-1), 5.04Ϫ5.06 (m, 2 H, H-
3, H-4), 5.73 (dd, 1 H, J2,3 ϭ 2.7 Hz, H-2), 7.22 (d, Jvic ϭ 8.5 Hz,
2 H, CH3Ar), 7.73 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar). 13C NMR
(CDCl3): δ ϭ 7.3 (SCH2CH3), 17.9 (CH3), 20.9Ϫ21.1 (3 COCH3),
21.8 (CH3Ar), 40.8 (SCH2CH3), 65.9 (C-2), 69.9, 71.3 (C-3, C-4),
76.8 (C-5), 89.6 (C-1), 126.3, 129.7 (2 ϫ 2 CH, CH3Ar), 141.1,
142.4 (2 C-arom. quat., CH3Ar), 169.3Ϫ170.2 (3 COCH3). HRMS
(C21H29NO9S2): calcd. 503.1283; found 503.1277.
Methyl 2,3,4-Tri-O-acetyl-S-(N-tosylimino)-1-thio-β-
L-fucopyrano-
side (12): Preparation from crystalline methyl 2,3,4-tri-O-acetyl-1- Ethyl 2,3,4,6-Tetra-O-acetyl-S-(N-tosylimino)-1-thio-β-
D
-galactofu-
thio-β--fucopyranoside[23] (62 mg, 0.193 mmol) according to Pro-
ranoside (15): Preparation from syrupy ethyl 2,3,4,6-tetra-O-acetyl-
cedure A and purification by column chromatography (petroleum 1-thio-β--galactofuranoside[25] (115 mg, 0.293 mmol) according to
ether/ethyl acetate, 2:8) gave amorphous 12 (47 mg, yield: 50%) in Procedure A and purification by column chromatography (petro-
1
the form of one epimer. [α]D ϭ ϩ104 (c ϭ 1.0, CHCl3). H NMR leum ether/ethyl acetate, 2:8) gave amorphous 15 (115 mg, yield
1
(CDCl3): δ ϭ 1.26 (d, Jvic ϭ 6.4 Hz, 3 H, CH3), 1.97, 2.11, 2.15 (3 70%) in the form of one epimer. [α]D ϭ Ϫ47 (c ϭ 1.8, CHCl3). H
s, 9 H, 3 COCH3), 2.39 (s, 3 H, CH3Ar), 2.68 (s, 3 H, SCH3), 3.97 NMR (CDCl3): δ ϭ 1.26 (t, Jvic ϭ 7.2 Hz, 3 H, SCH2CH3), 2.05,
(dq, 1 H, H-5), 4.54 (d, J1,2 ϭ 9.8 Hz, 1 H, H-1), 4.99 (t, 1 H, 2.11, 2.12 (3 s, 12 H, 4 COCH3), 2.38 (s, 3 H, CH3Ar), 2.88Ϫ3.10
J2,3 ϭ 9.8, H-2), 5.09 (dd 1 H, J3,4 ϭ 3.2 Hz, H-3), 5.29 (dd, 1 H, (m, 2 H, SCH2CH3), 4.09 (dd, 1 H, J5,6b ϭ 6.6, H-6b), 4.29 (dd, 1
J4,5 ϭ 0.9 Hz, H-4), 7.26 (d, Jvic ϭ 8.3 Hz, 2 H, CH3Ar), 7.75 (d, H, J5,6a ϭ 4.5, J6a,6b ϭ Ϫ12.2, H-6a), 4.31 (dd, 1 H, J4,5 ϭ 4.5 Hz,
Jvic ϭ 8.0 Hz, 2 H, CH3Ar). 13C NMR (CDCl3): δ ϭ 16.2 (CH3),
H-4), 5.10 (d, J1,2 ϭ 1.5 Hz, 1 H, H-1), 5.14 (dd, 1 H, J3,4 ϭ 3.6
20.6, 20.7, 20.9 (3 COCH3), 21.8 (CH3Ar), 25.6 (SCH3), 65.3 (C- Hz, H-3), 5.24Ϫ5.31 (m, 1 H, H-5), 5.66 (d, 1 H, J2,3 Ͻ 0.5, H-2),
4), 69.8 (C-3), 71.2 (C-2), 75.1 (C-5), 90.4 (C-1), 126.6, 129.7 (2 ϫ 7.24 (d, Jvic ϭ 7.9 Hz, 2 H, CH3Ar), 7.79 (d, Jvic ϭ 8.1 Hz, 2 H,
2 CH, CH3Ar), 141.4, 142.4 (2 C-arom. quat., CH3Ar), 169.9, CH3Ar). 13C NMR (CDCl3): δ ϭ 7.3 (SCH2CH3), 20.8Ϫ21.1 (4
170.4, 170.9 (3 COCH3). HRMS (C20H27NO9S2): calcd. 489.1126; COCH3), 21.8 (CH3Ar), 41.0 (SCH2CH3), 62.5 (C-6), 69.5 (C-3),
found 489.1114.
76.8 (C-5), 77.6 (C-2), 85.8 (C-4), 97.0 (C-1), 128.6, 129.6 (2 ϫ 2
Eur. J. Org. Chem. 2002, 171Ϫ180
177

´
F. Chery, S. Cassel, H. P. Wessel, P. Rollin
FULL PAPER
CH, CH3Ar), 141.2, 142.4 (2 C-arom. quat., CH3Ar), 168.8, 170.0, methyl 4,6-O-benzylidene-2-deoxy-α--glucopyranoside[31] (33 mg,
170.2, 170.8 (4 COCH3). HRMS (C23H31NO11S2): calcd. 561.1337; 0.124 mmol) as acceptor according to Procedure C (4 h; chromato-
found 561.1330.
graphy: petroleum ether/ethyl acetate, 6:4) furnished 22 (40 mg,
1
yield 54%). [α]2D0 ϭ ϩ27 (c ϭ 2.0, CHCl3). H NMR (CDCl3): δ ϭ
1,2:5,6-Di-O-isopropylidene-3-O-(2,3,4,6-tetra-O-benzyl-α- and -β-
1.78 (ddd, 1 H, J2Јb,3Ј ϭ 11.3, H-2Јb), 2.13 (dd, 1 H, J2Јa,3Ј ϭ 5.3,
J2Јa,2Јb ϭ Ϫ13.4, H-2Јa), 1.97, 1.99, 2.01 (3 s, 12 H, 4 COCH3),
D-glucopyranosyl)-α-D-glucofuranose (16): Treatment of the glycosyl
donor 4 with 1,2:5,6-di-O-isopropylidene-α--glucofuranose (50
mg, 0.192 mmol) as acceptor according to Procedure B (15 min)
and purification by column chromatography (petroleum ether/ethyl
acetate, 8:2) furnished 16 together with 1,2:3,5-di-O-isopropylid-
ene-6-O-(2,3,4,6-tetra-O-benzyl-α- and -β--glucopyranosyl)-α--
glucofuranose as a side-product (Table 3). The physical data were
in accordance with the literature.[26]
3.33 (s, 3 H, OMe), 3.44 (dt, 1 H, H-5), 3.65 (t, 1 H, J3Ј,4Ј ϭ J4Ј,5Ј
ϭ
9.4, H-4Ј), 3.72Ϫ3.82 (m, 2 H, H-6Јb, H-3Ј), 3.87 (dd, 1 H, J5,6b ϭ
2.3, H-6b), 4.08 (dd, 1 H, J5,6a ϭ 3.8, J6a,6b ϭ Ϫ12.1, H-6a), 4.16
(dt, 1 H, H-5Ј), 4.22 (m, 1 H, H-6Јa), 4.67 (d, J1,2 ϭ 7.8 Hz, 1 H,
H-1), 4.78 (d, 1 H, J1Ј,2Ј ϭ 3.4, H-1Ј), 4.96 (t, J2,3 ϭ 8.9 Hz, 1 H,
H-2), 5.06 (t, 1 H, H-4), 5.13(t, J3,4 ϭ 8.9 Hz, 1 H, H-3), 5.58 (s,
1 H, H-7Ј), 7.33Ϫ7.49 (m, 5 H, Ph). 13C NMR (CDCl3): δ ϭ
21.0Ϫ21.1 (4 COCH3), 36.5 (C-2Ј), 55.2 (OMe), 61.9 (C-6), 63.2
(C-3Ј,), 68.4 (C-2), 69.4 (C-6Ј), 71.1 (C-5Ј), 72.2 (C-4), 73.3 (C-
3), 75.2 (C-5), 82.3 (C-4Ј), 99.1 (C-1Ј), 101.1 (C-1), 101.9 (C-7Ј),
126.3Ϫ129.5 (5 CH, Ph), 139.8 (C-arom. quat., Ph), 171.6, 171.7,
172.7, 173.1 (4 COCH3). HRMS (C28H36O14): calcd. 596.2103;
found 596.2097.
1,2:3,4-Di-O-isopropylidene-6-O-(2,3,4,6-tetra-O-benzyl-α-
D-
glucopyranosyl)-α- and -β- -galactopyranose (17): Treatment of 4
D
with 1,2:3,4-di-O-isopropylidene-α--galactopyranose (55 mg,
0.211 mmol) as acceptor according to Procedure B (15 min; chro-
matography: petroleum ether/ethyl acetate, 7:3, 6:4 and 1:1) fur-
nished 17[27] (Table 3).
Methyl
3-O-(2,3,4,6-Tetra-O-acetyl-β-
D-glucopyranosyl)-4,6-O-
1,2:5,6-Di-O-isopropylidene-3-O-(2,3,4,6-tetra-O-acetyl-β-
glucopyranosyl)-α- -glucofuranose and 1,2:3,5-Di-O-isopropylidene-
6-O-(2,3,4,6-tetra-O-acetyl-β- -glucopyranosyl)-α- -glucofuranose
(18): Treatment of the glycosyl donor 1 with 1,2:5,6-di-O-isopropyl-
idene-α--glucofuranose (77 mg, 0.296 mmol) as acceptor accord-
ing to Procedure C (5 h; chromatography: petroleum ether/ethyl
acetate, 7:3, 6:4 and 1:1) furnished 18[28] (Table 4).
D-
benzylidene-2-deoxy-2-C-methyl-α-
D-altropyranoside (23): Treat-
D
ment of 1 with methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-α--
altropyranoside[32] (36 mg, 0.128 mmol) as acceptor according to
Procedure C (6 h; chromatography: toluene/ethyl acetate, 7:3) fur-
nished 23 (36 mg, yield 46%). [α]2D0 ϭ ϩ47 (c ϭ 1.7, CHCl3). 1H
NMR (CDCl3): δ ϭ 1.15 (d, 3 H, J ϭ 7.7, CH3), 1.98, 1.99, 2.01,
2.06 (4 s, 12 H, 4 COCH3), 2.38 (dd, 1 H, J2Ј,3Ј ϭ 2.6, 2Ј-H), 3.34
(s, 3 H, OMe), 3.60 (ddd, 1 H, J5,6a ϭ 2.9, J5,6b ϭ 4.1, 5-H), 3.72
D
D
1,2:3,4-Di-O-isopropylidene-6-O-(2,3,4,6-tetra-O-acetyl-β-
D-gluco-
pyranosyl)-α- -galactopyranose (19): Treatment of 1 with 1,2:3,4-
D
(t, 1 H, J5Ј,6bЈ ϭ 10.0, 6Ј-Hb), 3.81 (dd, 1 H, J3Ј,4Ј ϭ 2.6, J4Ј,5Ј
9.4, 4Ј-H), 3.99 (t, 1 H, 3Ј-H), 4.10 (dd, 1 H, J5Ј,6aЈ ϭ 5.1, J6aЈ,6bЈ
ϭ
di-O-isopropylidene-α--galactopyranose (79 mg, 0.303 mmol) as
acceptor according to Procedure C (4 h; chromatography: petro-
leum ether/ethyl acetate, 8:2) furnished 19[27] (Table 4).
ϭ
Ϫ10.0, 6Ј-Ha), 4.19 (ddd, 1 H, 5Ј-H), 4.10Ϫ4.36 (m, 2 H, 6-Ha, 6-
Hb), 4.39 (s, 1 H, 1Ј-H), 4.90 (d, 1 H, J1,2 ϭ 7.4, 1-H), 5.07 (t, 1
H, J3,4 ϭ 9.4, 4-H), 5.12 (t, 1 H, 3-H), 5.21(t, 1 H, J2,3 ϭ 9.4, 2-
H), 5.52 (s, 1 H, 7Ј-H), 7.33Ϫ7.57 (m, 5 H, Ph). 13C NMR (CDCl3):
δ ϭ 16.8 (CH3), 21.0Ϫ21.1 (4 COCH3), 40.2 (C-2Ј), 55.4 (OMe),
58.6 (C-5Ј), 62.4 (C-6Ј), 69.0 (C-5), 69.9 (C-6), 71.5 (C-4), 71.9 (C-
2), 73.1 (C-3), 76.1 (C-3Ј), 77.3 (C-4Ј), 100.9 (C-1), 102.6 (C-1Ј, C-
7Ј), 126.3Ϫ129.3 (5 CH, Ph), 137.5 (C-arom. quat., Ph), 169.3,
169.4, 170.4, 170.8 (4 COCH3). HRMS (C29H38O14): calcd.
610.2259; found 610.2251.
p-Methoxyphenyl 2,3,4,6-Tetra-O-acetyl-β-D-glucopyranoside (20):
Treatment of 1 with 4-methoxyphenol (13 mg, 0.105 mmol) as ac-
ceptor according to Procedure C (2.5 h; chromatography: petro-
leum ether/ethyl acetate, 7:3) furnished 20 (43 mg, yield 91%).[29]
5-O-(2,3,4,6-Tetra-O-acetyl-β-
1,2-O-isopropylidene-β- -fructopyranose (21): Treatment of 1 with
1,2-O-isopropylidene-3,4-di-O-benzoyl-β--fructopyranose[30]
(60
D-glucopyranosyl)-3,4-di-O-benzoyl-
D
mg, 0.140 mmol) as acceptor according to Procedure C (5 h; chro-
5-O-(2,3,4,6-Tetra-O-acetyl-β-
1,2-O-isopropylidene-β- -sorbopyranose (24): Treatment of 1 with
3,4-di-O-benzyl-1,2-O-isopropylidene-β--sorbopyranose[33]
(61
D-glucopyranosyl)-3,4-di-O-benzyl-
matography: petroleum ether/ethyl acetate, 6:4) furnished 21 as a
1
L
syrup (77 mg, yield 72%). [α]D ϭ Ϫ81 (c ϭ 3.6, CHCl3). H NMR
(CDCl3): δ ϭ 1.41, 1.51 (2 s, 6 H, 2 CH3 iPrd), 1.62, 2.03, 2.04 (3 s,
mg, 0.152 mmol) as acceptor according to Procedure C (3 h; chro-
12 H, 4 COCH3), 3.66Ϫ3.79 (dt, 1 H, H-5), 3.83 (dd, 1 H, J5Ј,6Јb
ϭ
matography: petroleum ether/ethyl acetate, 7:3) furnished 24 (72
2.9, H-6Јb), 4.04Ϫ4.09 (m, 2 H, H-6a, H-6b), 3.98 (d, 1 H, J1Јa,1Јb ϭ
Ϫ8.5, H-1Јb), 4.09 (d, 1 H, H-1Јa), 4.13 (d, 1 H, J5Ј,6Јa Ͻ 0.5,
1
mg, yield: 65%). [α]D ϭ Ϫ22 (c ϭ 3.6, CHCl3). H NMR (CDCl3):
δ ϭ 1.43, 1.48 (2 s, 6 H, 2 CH3 iPrd), 1.81, 1.99, 2.02, 2.08 (4 s, 12
H, 4 COCH3), 3.35 (d, J3,4 ϭ 8.9 Hz, 1 H, H-3), 3.65Ϫ3.84 (m, 5
H, H-4Ј, H-5, H-5Ј, H-6Јa, H-6Јb), 3.80 (d, 1 H, J1Јa,1Јb ϭ Ϫ8.5,
J
6Јa,6Јb ϭ Ϫ12.3, H-6Јa), 4.31 (dd, 1 H, H-2), 4.38Ϫ4.39 (m, 1 H, H-
5Ј), 4.80 (dd, 1 H, J4,5 ϭ 9.4 Hz, H-4), 5.07 (t, 1 H, J2,3 ϭ J3,4
ϭ
3.4 Hz, H-3), 5.48 (dd, 1 H, J4Ј,5Ј ϭ 3.4, H-4Ј), 5.57 (d, J1,2 ϭ 7.1
Hz, 1 H, H-1), 5.83 (d, 1 H, J3Ј,4Ј ϭ 10.4, H-3Ј), 7.29Ϫ7.38 (m, 2 H,
Bz), 7.44Ϫ7.51 (m, 4 H, Bz), 7.89Ϫ8.00 (m, 4 H, Bz). Ϫ13C NMR
(CDCl3): δ ϭ 21.2Ϫ22.4 (4 COCH3), 26.6, 26.9 (2 CH3, iPrd), 63.3
(C-6), 63.9 (C-6Ј), 67.5 (C-3Ј), 67.7 (C-5), 68.3 (C-4), 69.9 (C-5Ј),
70.4 (C-3), 71.8 (C-4Ј), 72.2 (C-1Ј), 73.8 (C-2), 97.4 (C-1), 106.8 (C-
2Ј), 114.4 (Cquat., iPrd), 124.0, 130.6 (2 C-arom. quat., Bz),
128.6Ϫ135.5 (10 CH Bz), 168.1, 168.2, 171.2, 171.7, 172.8 (4
COCH3, 2 CO Bz). HRMS (C37H42O17): calcd. 758.2419; found
758.2415.
H-1Јb), 3.89 (d, 1 H, H-1Јa), 4.12 (dd, 1 H, J5,6b ϭ 2.3, J6a,6b
ϭ
Ϫ12.1, H-6b), 4.24 (dd, 1 H, J5,6a ϭ 4.6, H-6a), 4.60 (d, 1 H, J ϭ
Ϫ11.5, CH2Ph), 4.77 (s, 2 H, CH2Ph), 4.85 (d, J1,2 ϭ 7.8 Hz, 1 H,
H-1), 4.90 (d, 1 H, J ϭ Ϫ11.5, CH2Ph), 5.02 (dd, 1 H, H-2), 5.06
(t, J4,5 ϭ 9.4 Hz, 1 H, H-4), 5.20 (t, 1 H, J2,3 ϭ J3,4 ϭ 9.4 Hz, H-
3), 7.24Ϫ7.38 (m, 10 H, 2 CH2Ph). 13C NMR (CDCl3): δ ϭ 20.7,
20.8, 20.9, 21.1 (4 COCH3), 26.5, 27.5 (2 CH3, iPrd), 62.3, 62.4 (C-
6, C-6Ј), 68.8 (C-4), 71.8, 72.1 (C-2, C-5), 73.4 (C-3), 75.7, 75.8 (2
CH2Ph), 78.5 (C-3Ј), 79.9, 83.1 (C-4Ј, C-5Ј), 101.4 (C-1), 105.2 (C-
2Ј), 112.6 (C-quat., iPrd), 126.3Ϫ130.1 (10 CH, 2 CH2Ph), 138.3,
138.6 (2 C-arom. quat., CH2Ph), 169.6, 169.8, 170.6, 170.9 (4
COCH3). HRMS (C37H46O15): calcd. 730.2834; found 730.2828.
Methyl
benzylidene-2-deoxy-α-
3-O-(2,3,4,6-Tetra-O-acetyl-β-
D
-glucopyranosyl)-4,6-O-
D-glucopyranoside (22): Treatment of 1 with
178
Eur. J. Org. Chem. 2002, 171Ϫ180

Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
FULL PAPER
Methyl 4-O-(2,3,4,6-Tetra-O-acetyl-β-
O-benzyl-α- -glucopyranoside (25): Treatment of 1 with methyl J1,2 Ͻ 0.5, H-1), 5.41 (m, 1 H, H-5), 5.50 (d, 1 H, J1Ј,2Ј ϭ 5.1, H-
2,3,6-tri-O-benzyl-α--glucopyranoside[34] (63 mg, 0.136 mmol) as 1Ј). 13C NMR (CDCl3): δ ϭ 20.7, 20.8, 20.9 (4 COCH3), 24.7, 24.9,
D-glucopyranosyl)-2,3,6-tri-
J3,4 ϭ 5.7, H-3), 5.06 (d, J2,3 ϭ 1.9 Hz, 1 H, H-2), 5.08 (s, 1 H,
D
acceptor according to Procedure C (4 h; chromatography: petro-
25.9, 26.1 (4 CH3, iPrd), 63.1 (C-6), 64.9 (C-6Ј), 65.5 (C-5Ј), 69.3
(C-5), 70.8, 70.5 (C-3, C-4Ј), 76.6 (C-3), 77.4 (C-4), 80.1 (C-2Ј),
81.1 (C-2), 96.2 (C-1Ј), 104.8 (C-1), 108.6, 109.3 (2 C-quat., iPrd),
169.6, 169.9, 170.1, 170.7 (4 COCH3). HRMS (C26H38O15): calcd.
590.2208; found 590.2202.
leum ether/ethyl acetate, 7:3) furnished 25 (98 mg, yield 91%).[35]
p-Methoxyphenyl 2,3,4,6-Tetra-O-acetyl-α-D-mannopyranoside (26):
Treatment of the glycosyl donor 8 with 4-methoxyphenol (30 mg,
0.241 mmol) as acceptor according to Procedure C (2.5 h; chroma-
tography: petroleum ether/ethyl acetate, 7:3) furnished 26 (66 mg,
yield 60%).[36]
1,2:3,4-Di-O-isopropylidene-6-O-(2,3,4,6-tetra-O-acetyl-α-
D-manno-
Acknowledgments
pyranosyl)-α- -galactopyranose (27): Treatment of 8 with 1,2:3,4-
D
di-O-isopropylidene-α--galactopyranose (48 mg, 0.184 mmol) as
acceptor according to Procedure C (5 h; chromatography: petro-
leum ether/ethyl acetate, 7:3) furnished 27 (92 mg, yield 85%).
[α]D ϭ ϩ3 (c ϭ 3.0, CHCl3). 1H NMR (CDCl3): δ ϭ 1.32, 1.40,
1.53 (3 s, 12 H, 4 CH3, iPrd), 1.96, 2.02, 2.08, 2.13 (4 s, 12 H, 4
COCH3), 3.69 (dd, 1 H, J5,6b ϭ 3.9, J6a,6b ϭ Ϫ10.2, H-6b), 3.77
(dd, 1 H, J5,6a ϭ 4.6, H-6a), 3.95 (dt, 1 H, J5Ј,6Јa ϭ J5Ј,6Јb ϭ 6.3,
H-5Ј), 4.03Ϫ4.14 (m, 2 H, H-5, H-6Јb), 4.22 (dd, 1 H, J4Ј,5Ј ϭ 1.9,
H-4Ј), 4.27Ϫ4.32 (m, 2 H, H-2Ј, H-6Јa), 4.60 (dd, 1 H, J2Ј,3Ј ϭ 2.4,
J3Ј,4Ј ϭ 7.9, H-3Ј), 4.84 (d, J1,2 ϭ 1.8 Hz, 1 H, H-1), 5.22Ϫ5.34 (m,
3 H, H-2, H-3, H-4), 5.48 (d, 1 H, J1Ј,2Ј ϭ 4.9, H-1Ј). 13C NMR
(CDCl3): δ ϭ 21.0, 21.1, 21.2, 21.3 (4 COCH3), 24.7, 25.3, 26.3,
26.5 (4 CH3, iPrd), 62.7(C-6Ј), 66.7 (C-5Ј), 67.4 (C-6), 68.9 (C-5),
66.4, 69.6, 69.8 (C-2, C-3, C-4), 70.9 (C-2Ј, C-3Ј), 71.2 (C-4Ј), 96.6
(C-1Ј), 98.2 (C-1), 109.1, 109.7 (2 C-quat., iPrd), 170.2, 170.3,
170.4, 171.1 (4 COCH3). HRMS (C26H38O15): calcd. 590.2208;
found 590.2211.
The authors wish to thank R. Keller and I. Plessis for skilful tech-
nical assistance. They are also grateful to Dr. J. C. Jacquinet, Dr.
`
T. Heidelberg and Dr. V. Ferrieres for useful comments.
[1] [1a]
K. Toshima, K. Tatsuta, Chem. Rev. 1993, 93,
1503Ϫ1531.[1b] B. G. Davis, J. Chem. Soc., Perkin Trans. 1
2000, 2137Ϫ2160.
[2]
P. J. Garegg, Adv. Carbohydr. Chem. 1997, 52, 179Ϫ205.
[3]
A. Marra, F. Gauffeny, P. Sinay¨, Tetrahedron 1991, 47,
5149Ϫ5160.
L. Yan, D. Kahne, J. Am. Chem. Soc. 1996, 118, 9239Ϫ9248,
and references cited therein.
[4]
[5]
D. Crich, S. Sun, J. Am. Chem. Soc. 1998, 120, 435Ϫ436.
[6]
S. Cassel, I. Plessis, H. P. Wessel, P. Rollin, Tetrahedron Lett.
1998, 39, 8097Ϫ8100.
[7]
T. L. Gilchrist, C. J. Moody, Chem. Rev. 1977, 77, 409Ϫ435.
[8]
C. R. Johnson, K. Mori, A. Nakanishi, J. Org. Chem. 1979,
44, 2065Ϫ2067.
P. S. Aujila, C. P. Baird, P. C. Taylor, H. Mauger, Y. Vallee,
p-Methoxyphenyl 2,3,4-Tri-O-acetyl-α-L-rhamnopyranoside (28):
[9]
´
Treatment of the glycosyl donor 13 with 4-methoxyphenol as ac-
ceptor (17 mg, 0.137 mmol) according to Procedure C (2.5 h; chro-
matography: petroleum ether/ethyl acetate, 8:2) furnished 28 (51
Tetrahedron Lett. 1997, 38, 7453Ϫ7456.
[10]
For a recent review on the synthesis and reactivity of sulfim-
ides, see: P. C. Taylor, Sulfur Rep. 1999, 21, 241Ϫ280 and ref.
cited.
1
mg, yield 94%). [α]D ϭ Ϫ61 (c ϭ 2.5, CHCl3). H NMR (CDCl3):
[11]
[12]
δ ϭ 1.2 (d, Jvic ϭ 6.4 Hz, 3 H, CH3), 2.02, 2.05, 2.17 (3 s, 9 H, 3
T. Buskas, P. J. Garegg, P. Konradsson, J.-L. Maloisel, Tetra-
hedron: Asymmetry 1994, 5, 2187Ϫ2194.
M. A. Nashed, C. W. Slife, M. Kiso, L. Anderson, Carbohydr.
Res. 1980, 82, 237Ϫ252.
H. Paulsen, Angew. Chem. Int. Ed. Engl. 1982, 21, 155Ϫ173.
T. Mukaiyama, T. Nakatsuta, S.-I. Shoda, Chem. Lett. 1979,
487Ϫ490.
COCH3), 3.76 (s, 3 H, OMe), 4.05 (dt, 1 H, H-5), 5.13 (t, J3,4
J4,5 ϭ 10.0 Hz, H-4), 5.33 (s, 1 H, J1,2 Ͻ 0.5, H-1), 5.41 (d, J2,3
ϭ
ϭ
3.4 Hz, 1 H, H-2), 5.49 (dd, 1 H, H-3), 6.82 (d, Jvic ϭ 9.1 Hz, 2 H,
PhOMe), 6.99 (d, Jvic ϭ 8.9 Hz, 2 H, PhOMe). 13C NMR (CDCl3):
δ ϭ 19.2 (CH3), 22.4, 22.5, 22.6 (3 COCH3), 57.3 (OMe), 68.7 (C-
5), 70.7 (C-3), 71.5 (C-2), 72.7 (C-4), 98.2 (C-1), 116.3, 119.3 (2 ϫ
2 CH, PhOMe), 151.6, 156.9 (2 C-arom. quat.), 171.6, 171.7, 171.8
(3 COCH3). HRMS (C19H24O9): calcd. 396.1419; found 396.1424.
[13]
[14]
[15]
A. Dondoni, A. Marra, M.-C. Sherrmann, A. Castani, F. San-
sone, R. Ungaro, Chem. Eur. J. 1997, 3, 1774Ϫ1782.
[16] [16a]R. R. Schmidt, M. Behrendt, A. Toepfer, Synlett 1990,
694Ϫ696.[16b] I. Braccini, C. Derouet, J. Esnault, C. Herve du
´
1,2:3,4-Di-O-isopropylidene-6-O-(2,3,4-tri-O-acetyl-α-
L-rhamno-
Penhoat, J.-M. Mallet, V. Michon, P. Sinay¨, Carbohydr. Res.
1993, 246, 23Ϫ41.[16c] M. Alaoui, A. J. Fairbanks, Chem. Com-
mun. 2001, 1406Ϫ1407.
G. Vic, J. J. Hastings, O. W. Howarth, D. H. G. Crout, Tetra-
hedron: Asymmetry 1996, 7, 709Ϫ720.
F. Weygand, H. Ziemann, Justus Liebigs Ann. Chem. 1962,
657, 179Ϫ198.
Z. Pakulski, D. Pierozynski, A. Zamojski, Tetrahedron 1994,
50, 2975Ϫ2992.
S.-F. Lu, Q. O’yang, Z.-W. Guo, B. Yu, Y.-Z. Hui, J. Org.
Chem. 1997, 62, 8400Ϫ8405.
M.-O. Contour, J. Defaye, M. Little, E. Wong, Carbohydr. Res.
1989, 193, 283Ϫ287.
pyranosyl)-α- -galactopyranose (29): Treatment of 13 with 1,2:3,4-
D
di-O-isopropylidene-α--galactopyranose (52 mg, 0.200 mmol) as
acceptor according to Procedure C (5 h; chromatography: petro-
leum ether/ethyl acetate, 7:3) furnished 29 (53 mg, yield 50%).[37]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
1,2:3,4-Di-O-isopropylidene-6-O-(2,3,4,6-tetra-O-acetyl-β-
D-
galactofuranosyl)-α- -galactopyranose (30): Treatment of the glyco-
D
syl donor 15 with 1,2:3,4-di-O-isopropylidene-α--galactopyranose
(27 mg, 0.104 mmol) as acceptor according to Procedure C (3 h;
chromatography: petroleum ether/ethyl acetate, 6:4) furnished 30
(51 mg, yield 83%). [α]D ϭ Ϫ70 (c ϭ 1.0, CHCl3). 1H NMR
(CDCl3): δ ϭ 1.31, 1.32, 1.43, 1.52 (4 s, 12 H, 4 CH3, iPrd), 2.04,
2.06, 2.08, 2.12 (4 s, 12 H, 4 COCH3), 3.57 (dd, 1 H, J5Ј,6Јb ϭ 6.6,
J6Јa,6Јb ϭ Ϫ9.6, H-6Јb), 3.84 (dd, 1 H, J5Ј,6Јa ϭ 6.6, H-6Јa), 3.96
(m, 1 H, H-5Ј), 4.17 (dd, 1 H, J5,6b ϭ 7.7, H-6b), 4.24 (dd, 1 H,
J4Ј,5Ј ϭ 1.9, J3Ј,4Ј ϭ 7.9, H-4Ј), 4.29 (dd, 1 H, J4,5 ϭ 7.5 Hz, H-4),
4.30 (dd, 1 H, H-2Ј), 4.37 (dd, 1 H, J5,6a ϭ 3.6, J6a,6b ϭ Ϫ11.9, H-
6a), 4.59 (dd, 1 H, J2Ј,3Ј ϭ 2.3, J3Ј,4Ј ϭ 7.9, H-3Ј), 4.94 (dd, 1 H,
R. I. El-Sokkary, B. A. Silwanis, M. A. Nashed, H. Paulsen,
Carbohydr. Res. 1990, 203, 319Ϫ323.
S. Sato, Y. Ito, T. Nukada, T. Nakahara, T. Ogawa, Carbohydr.
Res. 1987, 167, 197Ϫ210.
[24]
[25]
`
´
A. Borbas, A. Liptak, Carbohydr. Res. 1993, 241, 99Ϫ116.
`
M. Gelin, V. Ferrieres, D. Plusquellec, Eur. J. Org. Chem.
2000, 1423Ϫ1431.
Eur. J. Org. Chem. 2002, 171Ϫ180
179

´
F. Chery, S. Cassel, H. P. Wessel, P. Rollin
FULL PAPER
[26]
[33]
A. K. Misra, N. Roy, Carbohydr. Res. 1995, 278, 103Ϫ111.
A. Tatiboue¨t, M. Lefoix, J. Nadolny, O. R. Martin, P. Rollin,
J. Yang, G. D. Holman, Carbohydr. Res. 2001, 333, 327Ϫ334.
P. J. Garegg, H. Hultberg, Carbohydr. Res. 1981, 93, C10ϪC11.
P. Konradsson, D. R. Mootoo, R. E. McDevitt, B. Fraser-Reid,
J. Chem. Soc., Chem. Commun. 1990, 270Ϫ272.
M. Mori, Y. Ito, T. Ogawa, Carbohydr. Res. 1989, 192,
131Ϫ146.
L. V. Backinowsky, Y. E. Tsvetkov, N. F. Balan, N. E. Byra-
mova, N. K. Kochetkov, Carbohydr. Res. 1980, 85, 209Ϫ222.
Received August 2, 2001
[27]
M. Kreuzer, J. Thiem, Carbohydr. Res. 1986, 149, 347Ϫ361.
[28]
[34]
[35]
´
´ ´
´
A. Liptak, P. Nanasi, A. Neszmelyi, H. Wagner, Carbohydr.
Res. 1980, 86, 133Ϫ136.
[29]
[30]
Z. Zhang, G. Magnusson, Carbohydr. Res. 1996, 295, 41Ϫ55.
F. W. Lichtenthaler, W. Dolesschal, S. Hahn, Liebigs Ann.
Chem. 1985, 2454Ϫ2464.
T. Yoshisuke, N. Makoto, I. Yoko, Chem. Pharm. Bull. 1991,
39, 1983Ϫ1989.
[36]
[37]
[31]
[32]
K. Jones, W. W. Wood, J. Chem. Soc., Perkin Trans. 1 1987,
537Ϫ545.
[O01373]
180
Eur. J. Org. Chem. 2002, 171Ϫ180