Palladium-catalyzed synthesis of bis-glycosides of but-2-ene-1,4-diol, butane-1,4-diol, and 1,2-bis(propenyl)benzene

Article abstract of DOI:10.1081/CAR-120016853

Palladium(0)-catalyzed reaction of various carbohydrates derived from glucofuranose, mannofuranose, ribofuranose, glucopyranose, and glucosamine, beating a free hydroxyl group, with 1,4-bis-(methoxycarbonyloxy)but-2-ene afforded the corresponding bis-glyc

Full text of DOI:10.1081/CAR-120016853

Journal of Carbohydrate Chemistry
ISSN: 0732-8303 (Print) 1532-2327 (Online) Journal homepage: http://www.tandfonline.com/loi/lcar20
PALLADIUM-CATALYZED SYNTHESIS OF BIS-
GLYCOSIDES OF BUT-2-ENE-1,4-DIOL, BUTANE-1,4-
DIOL AND 1,2-BIS(PROPENYL)BENZENE
Denis Sinou , Paul Lhoste , Nathalie Pichon , Boguslaw Kryczka , Stanislaw
Porwanski & Annia Zawisza
To cite this article: Denis Sinou , Paul Lhoste , Nathalie Pichon , Boguslaw Kryczka , Stanislaw
Porwanski & Annia Zawisza (2002) PALLADIUM-CATALYZED SYNTHESIS OF BIS-GLYCOSIDES
OF BUT-2-ENE-1,4-DIOL, BUTANE-1,4-DIOL AND 1,2-BIS(PROPENYL)BENZENE, Journal of
Carbohydrate Chemistry, 21:6, 545-558
To link to this article: http://dx.doi.org/10.1081/CAR-120016853
Published online: 16 Aug 2006.
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JOURNAL OF CARBOHYDRATE CHEMISTRY
Vol. 21, No. 6, pp. 545–558, 2002
PALLADIUM-CATALYZED SYNTHESIS OF
BIS-GLYCOSIDES OF BUT-2-ENE-1,4-DIOL,
BUTANE-1,4-DIOL, AND
1,2-BIS(PROPENYL)BENZENE
1
1
Denis Sinou,1, Paul Lhoste, Nathalie Pichon,
*
Boguslaw Kryczka,2 Stanislaw Porwanski,2 and Annia Zawisza2
1Laboratoire de Synthe`se Asyme´trique, associe´ au CNRS, CPE Lyon,
Universite´ Claude Bernard Lyon 1, 43, Boulevard du 11 November 1918,
69622 Villeurbanne Ce´dex, France
2Department of Organic and Applied Chemistry, University of Lodz,
ul. Narutowicza 68, 90-136 Lodz, Poland
ABSTRACT
Palladium(0)-catalyzed reaction of various carbohydrates derived from
glucofuranose, mannofuranose, ribofuranose, glucopyranose, and glucosa-
mine, bearing a free hydroxyl group, with 1,4-bis-(methoxycarbonyloxy)but-
2-ene afforded the corresponding bis-glycosides of butene-1,4-diol.
Hydrogenation in the presence of palladium on charcoal of these unsaturated
compounds led to the formation of the bis-glycosides of butane-1,4-diol.
The condensation was successfully extended to the bis-carbonate of 1,2-bis-
[(1-hydroxy)propen-2-yl]benzene and derivatives of glucofuranose, ribofur-
anose and glucosamine.
Key Words: Spacer-linked disaccharides; Palladium; Butene-1,2-diol;
1,2-bis-[(1-Hydroxy)propen-2-yl]benzene
*
Corresponding author. E-mail: sinou@univ-lyon1.fr
545
DOI: 10.1081/CAR-120016853
Copyright D 2002 by Marcel Dekker, Inc.
0732-8303 (Print); 1532-2327 (Online)
www.dekker.com

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546
SINOU ET AL.
INTRODUCTION
Synthesis of spacer-modified disaccharides has attracted considerable attention
during the last years.[1] This interest is mainly due to the biological importance of car-
bohydrates in mediating a host of biological responses. This implication of carbohydrates
in molecular recognition processes has prompted researchers to prepare complex oli-
gosaccharides as tools for the study of the binding modes of various protein–carbohydrate
interactions. Another alternative is the synthesis of oligosaccharide mimics which may
offer a more flexible access to potential biological compounds. For example, a homo-
logous series of 1,10-bis(2-acetamido-2-deoxy-b-glucopyranosyloxy)alkanes were pre-
pared by Lehmann’s group[2,3] in order to study the mechanism of galactosylation of
b-galactosyltransferase. An access to various spacer-linked 1,1’-bis-and 1,1’,1@-tris-b-
glycosides was described by Patch et al.,[4] and to anomeric dimaltosides of alkanediols
by Tsuzuki and Tsuchiya.[5] More recently, various O- and C-allyl and O-pentenyl D-
galactopyranoside and lactoside homodimers were obtained by using ruthenium catalyzed
olefin metathesis.[6–8] These spacer-linked carbohydrates are also precursors of gemini
surfactants[9,10] or of various carbohydrate-based macrocycles.[11,12]
We have previously shown that palladium-catalyzed O-alkylation of unsaturated
carbohydrates by various glycosides with free hydroxyl groups provided an easy access
to various disaccharides. Following our continuing interest in the use of organometallic
catalysis in the carbohydrate field, we report here the application of this palladium-
catalyzed methodology for the synthesis of various spacer-linked disaccharides.[13–17]
Scheme 1. Palladium-catalyzed synthesis of bis-glycosides of butene-1,4-diol. Reagents: i:
Pd2(dba)3, dppb, THF, 25 °C; ii: H2, Pd/C 10%, AcOEt, 25 °C.

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PALLADIUM-CATALYZED SYNTHESIS
547
Scheme 2. Mechanism of the formation of the disaccharides.
RESULTS AND DISCUSSION
In our previous studies, we performed the palladium-catalyzed reaction between
the bis-allylic carbonate 2 and various carbohydrates 1a–e having a free hydroxyl
group on the tetrahydrofuran ring at 60°C in the presence of a catalytic amount of
tris(dibenzylideneacetone)dipalladium [Pd2(dba)3] and 1,4-bis(diphenylphosphino)butane
(dppb) (Scheme 1).
The proposed mechanism of formation of the disaccharides 3 is described in
Scheme 2. Oxidative addition of the bis-carbonate 2 to the palladium complex would
give the p-allyl palladium intermediate A. Hydrogen exchange between methoxide ion
and the hydroxyl group of the carbohydrate, followed by attack of the new oxo-anion
formed, is thought to afford the p-palladium complex B. A second oxidative addition
on the palladium would give the new p-allyl palladium complex C, whose attack by a
second molecule of carbohydrate then would lead to the unsaturated bis-saccharide 3.
We first used the bis-carbonate 2 derived from butene-1,2-diol as the p-allyl
precursor and as oxygen nucleophiles various carbohydrates 1a–e (Scheme 1). The
results obtained in these condensations are summarized in Table 1.
1,2;5,6-Di-O-isopropylidene-a-D-glucofuranose (1a) reacted with the bis-carbon-
ate 2 under the standard conditions to give the unsaturated disaccharide 3a in 29%
yield after column chromatography as a 9:1 mixture of the two stereoisomers E/Z. The
Table 1. Palladium-Catalyzed Condensation of Carbonates 2 and 7 with Various Carbohydrates
Carbonate
Carbohydrate
Yield (%)
Anomers (%)
2
1a
1b
1c
1d
1e
1b
1c
1e
26
38
52
56
54
38
63
59
–
a,a (100)
b,b/a,b (80/20)
a,a/a,b (50/50)
a,a/a,b (90/10)
a,a (100)
b,b/a,b (75/25)
a,a/a,b (70/30)
7

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548
SINOU ET AL.
Scheme 3. Palladium-catalyzed synthesis of bis-glycosides of 1,2-bis-[(1-hydroxy)propen-2-yl]
benzene. Reagents: i: CH2 = CHMgBr, Et2O, then H2O; ii: ClCO2CH3, C5H5N, CH2Cl2, 25 °C; iii:
SuOH, Pd2(dba)3, dppb, THF, 25 °C; iv: H2, Pd/C 10%, AcOEt, 25 °C.
presence of E/Z isomers was confirmed from the 13C NMR data; we observed two
signals for the allylic carbon atom, the signal of the E-isomer (d 70.2 ppm) being at
lower field than the signal of the Z-isomer (d 66.0 ppm). Reduction of the double bond
of compound 3a in the presence of palladium on charcoal as the catalyst gave the
saturated disaccharide 4a quantitatively.
Reaction of the furanoses 1b and 1c, namely 2,3;5,6-di-O-isopropylidene-D-man-
nofuranose and 2,3,5-tri-O-acetyl-D-ribofuranose, having a free hydroxyl group at the
anomeric position, with bis-carbonate 2 gave the corresponding disaccharides 3b and 3c
in 38% and 52% yield, respectively. While bis-saccharide 3b was obtained as the single
a,a anomer and as an E/Z mixture (83:17), bis-saccharide 3c was an a,b/b,b mixture in a
1:4 ratio.
When the reaction was performed using the pyranoses 1d and 1e, namely 2,3,4,6-
tetra-O-acetyl-D-glucopyranose and 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopy-
ranose, bis-saccharides 3d and 3e were obtained in 56% and 59% yields, respectively.
Disaccharide 3d was a 1:1 mixture of the a,a and a,b anomers, while disaccharide 3e
was a 9:1 mixture of the two a,a and a,b anomers.
We then extended this coupling reaction to another allylic bis-carbonate 7 obtained
by reaction of the corresponding diol 6 with methyl chloroformate in the presence of
pyridine, in order to obtain potentially complexing molecules (Scheme 3). Coupling of
bis-carbonate 7 with 2,3;5,6-di-O-isopropylidene-D-mannofuranose gave the bis-sac-
charide 8b in 38% yield as the unique a,a anomer having the E stereochemistry. On the

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PALLADIUM-CATALYZED SYNTHESIS
549
other hand, when the coupling was performed with 2,3,5-tri-O-acetyl-D-ribofuranose and
2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranose as the carbohydrates, bis-sac-
charides 8c and 8e were obtained in 63 and 59% yield, respectively. Compound 8c was a
3:1 mixture of the b,b and a,b anomers with the E stereochemistry, while compound 8e
was a 7:3 mixture of a,a and a,b anomers, also with the E stereochemistry.
The determination of the anomeric configuration of the disaccharides was mainly
1
based on H and 13C NMR spectroscopic data, in some cases after hydrogenation of the
corresponding unsaturated disaccharides.
The a-anomeric configuration of compounds 3b and 8b was readily derived from
1
the H NMR data; the coupling constants J1,2 ꢀ 0 Hz for the anomeric proton at d 5.00,
5.02, and 5.10 ppm, for (Z)-3b, (E)-3b, and 8b, respectively, are characteristic of the a
configuration in the mannofuranose series.[18,19] The a,a configuration was also
confirmed from the H NMR data of the saturated compound 4b, exhibiting again a
1
unique broad singlet for the anomeric proton at d 4.97 ppm.
Compound 3b was an 83:17 mixture of E/Z stereoisomers, as deduced from the
1H NMR spectrum, the major isomer exhibiting two signals for the H-1 and H-2
protons at d 5.02 and 4.61 ppm, respectively, while the minor one exhibited two signals
at d 5.00 and 4.58 ppm, respectively. The E/Z stereochemistry was assigned from the
13C NMR data; the signal of the allylic carbon atom of the major isomer E is at lower
field (d 66.9 ppm) than the signal of the minor isomer Z (d 62.6 ppm). For disaccharide
8b, the stereochemistry at the double bond was E, according to the coupling constant
J = 15.7 Hz observed for the ethylenic proton at d 6.87 ppm.
For disaccharide 3c, the signals of the anomeric protons appeared at d 5.00 and
5.04 ppm in a 8:1 ratio as two broad singlets, characteristic of a cis arrangement of H-1
and H-2, thus indicating a b configuration in the ribofuranoside series;[20,21] the signal of
the minor isomer corresponding to the a configuration appeared together with the H-2
and H-3 signals. We proposed for compound 3c an 8:2 mixture of b,b and b,a anomers,
this assignment being also in agreement with the stereoselectivity previously observed in
quite similar alkylation reactions.[15] These assignments were confirmed by the 1H NMR
data of the saturated compound 4c. We observed two broad singlets for H-1 at d 4.96
and 4.99 ppm in a ratio 8:1, and a sole doublet at d 5.23 ppm with a coupling constant
J1,2 = 5.6 Hz in a ratio 1:8 compared to the signal at d 4.96 ppm, characteristic of a b,b
and b,a configuration in the ribofuranose series,[20,21] respectively. It is to be noticed
that the relative chemical shifts for C-1 at d 104.9, 105.2, and 105.4 for anomers a, b,
and b, respectively, are in agreement with the literature data for such compounds, as
well as the chemical shifts for C-5 and OCH2.[22] The E stereochemistry was assigned at
the double bond of compound 3c since only one stereoisomer was detected.
For disaccharide 8c, the signal of the anomeric proton appeared at d 5.11 ppm for the
major anomer as a broad singlet, characteristic of a b configuration, and at d 5.26 as a
doublet (J1,2 =4.4 Hz) for the minor anomer, characteristic of an a configuration.[20,21]
These assignments were confirmed from the 13C NMR spectra, with the signal of the
anomeric carbon at d 99.6 ppm for the minor isomer, and at d 104.3 ppm for the major one,
characteristic of an a and b configuration, respectively.[22] The E stereochemistry of the
double bond was assigned from the coupling constant J =15.8 Hz of the ethylenic protons.
The 13C NMR spectrum of the saturated compound 4c also confirmed these assignments,
the signal for the anomeric carbon appearing at d 100.6 and 105.3 ppm for the a and the b
configuration, respectively.

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550
SINOU ET AL.
Bis-carbohydrate 3d was a 1:1 mixture of a,a and a,b anomers. The signal in the
1H NMR spectrum of the anomeric proton for the anomer b appeared as a doublet at d
4.56 ppm with a coupling constant J1,2 =7.7 Hz. When the anomeric proton for the
anomer a appeared together with the H-4 signal of anomer a and the H-2 signal of
anomer b, the H-2 signal for the a anomer appeared as a doublet of doublets at d 4.89
ppm, with a coupling constant J1,2 =3.7 Hz.[20,23] The same values were observed for
the reduced product 4d, with a coupling constant J1,2 = 7.4 Hz, and 3.7 Hz, for the b
and a anomers, respectively.
The 13C spectrum of 3d is in agreement with this assignment. The signals
corresponding to the anomeric carbon for 3d were observed at d 99.7 ppm for the b
anomer, and at d 94.8 and 95.1 ppm for the a anomer, the last one being the major
signal. The signal of C-5 appeared at d 67.4 and 71.8 ppm for the a and b anomers,
respectively. The same trends were also observed for the saturated bis-carbohydrate 4d;
the minor signals, corresponding to the b anomer, appeared at higher field (d 71.7 and
100.7 ppm for C-5 and C-1, respectively), than those of the major one corresponding to
the a anomer (d 67.2 and 95.8 ppm for C-5 and C-1, respectively).
Unsaturated bis-saccharide 3e is a 9:1 mixture of a,a/b,b anomers. This as-
signment was mainly based on 1H NMR spectral data; the signal of the anomeric
proton appeared at d 4.90 ppm as a doublet (J1,2 =3.5 Hz) for the major isomer, and as
two doublets at d 4.86 (J1,2 = 10.0 Hz) and 4.92 ppm (J1,2 = 3.5 Hz) for the minor
one.[24] This assignment was confirmed by reduction of 3e to the saturated bis-
1
carbohydrate 4e; the H NMR spectrum of 4e exhibited a unique doublet at d 4.87 ppm
with a coupling constant J1,2 = 3.7 Hz for the major isomer, characteristic of the a,a
configuration, while the minor isomer exhibited two doublets at d 4.77 ppm (J1,2 =9.2
Hz) and 4.82 ppm (J1,2 = 3.7 Hz), characteristic of a b and a configuration, respectively.
The a,a and a,b configuration for bis-saccharide 8e was also based on the signal of
the anomeric proton, as well as for the saturated disaccharide 9e. The major isomer
exhibited a doublet for the anomeric proton at d 4.96 ppm with a coupling constant
J1,2 =3.3 Hz, characteristic of an a configuration, whereas the minor isomer exhibited two
doublets at d 4.76 ppm (J1,2 =9.2 Hz) and d 4.96 ppm (J1,2 =3.3 Hz), characteristic of a b
and a configuration, respectively.[24] The anomeric signal for the saturated product 9e
appeared at d 4.84 ppm (J1,2 =3.3 Hz) and 4.70 ppm (J1,2 =9.2 Hz) for the a and b
anomers, respectively. The E configuration was assigned to the double bond of compound
8e based on the coupling constant observed for the ethylenic proton (J = 15.4 Hz).
CONCLUSION
In this paper, we have shown that diglycosides of butene-1,4-diol and butane-1,4-
diol could be obtained in moderate to good yields starting from the bis-carbonate of
butene-1,4-diol and various carbohydrates bearing a free hydroxyl group, such as 1,
2;5,6-di-O-isopropylidene-a-D-glucofuranose (1a), 2,3;5,6-di-O-isopropylidene-a-D-man-
nofuranose (1b), 2,3,5-tri-O-acetyl-D-ribofuranose (1c), 2,3,4,6-tetra-O-acetyl-D-gluco-
pyranose (1d), and 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranose (1e). Re-
duction of the double bond afforded disaccharides bearing a butyl moiety as a spacer.
This methodology was successfully extended to the bis-carbonate of 1,2-bis-[(1-hy-
droxy)propen-2-yl]benzene and 2,3;5,6-di-O-isopropylidene-a-D-mannofuranose, 2,3,5-
tri-O-acetyl-D-ribofuranose, and 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyra-

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PALLADIUM-CATALYZED SYNTHESIS
551
nose. Work is in progress in order to use this methodology for the introduction of
longer spacers.
EXPERIMENTAL
General Methods. All reactions were monitored by thin-layer chromatography
carried out on 0.25 mm silica gel plates (60 F-254, Merck). Compounds were vis-
ualized under UV light (254 nm) or by spraying with an H2SO4 solution and heating.
Column chromatography was performed on silica gel 60 (40–63 mesh, Merck). NMR
spectra were recorded on Bruker AC 200 and AM 300 spectrometers, and chemical
shifts are given in ppm on the d scale from internal tetramethylsilane. Reactions in-
volving palladium complexes were carried out in a Schlenk tube under a nitrogen
atmosphere. THF was distilled from sodium/benzophenone and stored under a nitrogen
atmosphere. Pd2(dba)3, 1,4-bis(diphenylphosphino)butane, 1,2;5,6-di-O-isopropylidene-
a-D-glucofuranose (1a), 2,3;5,6-di-O-isopropylidene-a-D-mannofuranose (1b) are from
commercial sources. 2,3,5-Tri-O-acetyl-D-ribofuranose (1c), 2,3,4,6-tetra-O-acetyl-D-
glucopyranose (1d) and 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranose (1e)
were prepared from the corresponding acetates according to the literature procedure.[25]
1,2-Bis-[1-(methoxycarbonyloxy)propen-2-yl]benzene (7). To a 1.0 M solution
of vinylmagnesium bromide in tetrahydrofuran (60 mL, 60 mmol) was added slowly
phthalic dicarboxaldehyde (5) (2.7 g, 20 mmol) dissolved in tetrahydrofuran (7 mL).
After being stirred for 16 h, the solution was treated with cold water (10 mL), and the
organic product was extracted with diethyl ether (2 Â 20 mL). Evaporation of the solvent
followed by flash chromatography of the residue using petroleum ether/ethyl acetate
(1:1) as the eluent gave 1.33 g of diol 6 as a 3:2 mixture of the diastereoisomers (yield
35%). Oil; Rf 0.55; 1H NMR (200 MHz, CDCl3) d 2.97 (bs, 2H, OH), 5.25 (dm, J =10.5
Hz, 2H, CH2), 5.37 (dm, J =17.4 Hz, 2H, CH2), 5.55 (bd, 2H, OCH <), 6.01–6.25
(m, 2H, CH ), 7.30–7.50 (m, 4H, C6H4); 13C (50 MHz, CDCl3) d 70.3 (CHOmin),
72.5 (CHOmaj), 115.0 ( CH2maj), 115.4 ( CH2min), 127.4, 128.3, 128.5, 139.2, 139.5,
140.1, and 140.3 (C6H4, CH ). To a solution of this crude diol 6 (1.2 g, 6.3 mmol)
and pyridine (1.25 g, 15.8 mmol) in CH2Cl2 (100 mL) was added slowly methyl
chloroformiate (1.5 g, 15.8 mmol) at 0°C. After stirring at room temperature for 4 h
the solution was filtered and washed with an aqueous solution of copper sulfate
(2 Â 100 mL). Evaporation of the solvent followed by flash-chromatography of the
residual oil on silica using a mixture of ethyl acetate/petroleum ether (2:7) as the eluent
gave the bis-carbonate 7 as a 3:2 mixture of two diastereoisomers (950 mg, 55% yield).
1
Rf 0.54; H NMR (200 MHz, CDCl3) d 3.76 (s, 2.4H, CH3), 3.78 (s, 3.6H, CH3), 5.23–
5.39 (m, 4H, CH2), 5.99–6.18 (m, 2H, CH ), 6.43–6.47(m, 2H, OCH <), 7.33–
7.48 (m, 4H, C6H4); 13C (50 MHz, CDCl3) d 54.8 (CH3), 76.1 (CHOmin), 76.5 (CHOmaj),
117.4 ( CH2min), 117.8 ( CH2maj), 127.9 (m), 128.0 (maj), 128.8 (maj), 128.8 (min),
135.3 (min), 135.6 (min), 136.0 (maj) and 136.1 (min) (C6H4, CH ), 154.9 (CO).
Anal. Calcd for C16H18O6 (306.32): C, 62.74; H, 5.92. Found: C, 62.56; H, 5.85.
General procedure for palladium-catalyzed O-alkylation Reaction. The
catalyst was prepared by stirring for 1 h Pd2(dba)3 (22.9 mg, 0.025 mmol) and dppb
(42.6 mg, 0.1 mmol) in tetrahydrofuran (5 mL) in a Schlenk tube under argon. This

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552
SINOU ET AL.
solution was added under argon to a Schlenk tube containing the biscarbonate 2
(102 mg, 0.5 mmol), or 7 (153 mg, 0.5 mmol), and the carbohydrate derivative 1
(1.44 mmol) in tetrahydrofuran (5 mL). The solution was stirred at 60°C, and the
reaction was followed by TLC. After disappearance of the starting biscarbonate, the
solvent was evaporated, and the residue was purified by silica gel chromatography to
give the bis-saccharides 3 or 8.
(E/Z)-1,4-Bis-O-(1,2;5,6-di-O-isopropylidene- -D-glucofuranosid-3-yl)but-
2-enediol (3a). Yield: 83 mg (29%); oil; Rf 0.22 (CH2Cl2/petroleum ether/diethyl ether
1
4:3:1); H NMR (200 MHz, CDCl3) d 1.32 (s, 6H, CH3), 1.36 (s, 6H, CH3), 1.42 (s, 6H,
CH3), 1.50 (s, 6H, CH3), 3.93 (d, 2H, J = 2.9 Hz, H-3), 4.00 (dd, 2H, J =8.7, 5.8 Hz, H-6),
3.90–4.25 (m, 8H, H-4, H-6, OCH2CH ), 4.31 (ddd, 2H, J =7.8, 5.9, 5.9 Hz, H-5), 4.54 (d,
2H, J = 3.6 Hz, H-2), 5.74 (t, 0.2 H, J = 3.6 Hz, CH (Z)), 5.81 (t, 1.8H, J = 2.8 Hz, CH
(E)), 5.87 (d, 2H, J =3.6 Hz, H-1); 13C (50 MHz, CDCl3) d 25.4 (CH3), 26.2 (CH3), 26.8
(2 Â CH3), 66.0 (OCH2CH (Z)), 67.3 (C-6), 70.2 (OCH2CH (E)), 72.4 (C-5), 81.1 and
81.4 (C-3, C-4), 82.7 (C-2), 105.2 (C-1), 108.9 (CMe2), 111.7 (CMe2), 128.8 ( CH-(Z)),
129.2 ( CH-(E)).
Anal. Calcd for C28H44O12 (572.65): C, 58.73; H, 7.74. Found: C, 58.79; H, 7.90.
(E/Z)-1,4-Bis(2,3;5,6-di-O-isopropylidene- -D-mannofuranosyloxy)but-2-ene
1
(3b). Yield: 163 mg (57%); oil; Rf 0.55 (ethyl acetate/petroleum ether 2:3); H NMR
(300 MHz, CDCl3) d 1.33 (s, 6H, CH3), 1.38 (s, 6H, CH3), 1.46 (s, 6H, CH3), 1.47 (s,
6H, CH3), 3.71 (dd, 2H, J =7.8, 3.6 Hz, H-4), 4.03 (dd, 2H, J =8.7, 4.3 Hz, H-6), 4.11
(dd, 2H, J =8.7, 6.3 Hz, H-6), 3.80–4.20 (m, 4H, OCH2CH ), 4.40 (ddd, 2H, J =7.8,
6.3, 4.3 Hz, H-5), 4.58 (d, 0.17 Â 2H, J = 5.9 Hz, H-2 (Z)), 4.61 (d, 0.83 Â 2H, J =5.9
Hz, H-2 (E)), 4.77 (dd, 2H, J = 5.9, 3.6 Hz, H-3), 5.00 (s, 0.17 Â 2H, H-1 (Z)), 5.02
(s, 0.83 Â 2H, H-1 (E)), 5.71 (dd, 0.17 Â 2H, J = 4.0, 4.0 Hz, = CH-(Z)), 5.78 (dd, 0.83 Â
2H, J =2.9, 2.9 Hz, CH-(E)); 13C (50 MHz, CDCl3) d 24.5 (CH3), 25.2 (CH3), 25.9
(CH3), 26.9 (CH3), 62.6 (OCH2CH (Z)), 66.8 (C-6), 66.9 (OCH2CH (E)), 73.1
(C-5), 79.5 and 80.4 (C-2, C-3), 85.1 (C-4), 105.7 (C-1), 109.2 (CMe2), 112.6 (CMe2),
128.9 ( CH-(E)), 129.0 ( CH-(Z)).
Anal. Calcd for C28H44O12 (572.65): C, 58.73; H, 7.74. Found: C, 58.79; H, 7.90.
(E)-1,4-Bis[2,3,5-tri-O-acetyl-D-ribofuranosyloxy)but-2-ene(3c). Yield:157mg
(52%) (as a 1:4 mixture of the a,b/b,b anomers); oil; Rf 0.51 (ethyl acetate/petroleum
1
ether 2:1); H NMR (300 MHz, CDCl3) d 2.03 (s, 6H, CH3), 2.06 (s, 4.8H, CH3), 2.07
(s, 1.2H, CH3), 2.08 (s, 6H, CH3), 3.65–3.80 (m, 2H, OCH2), 3.90–4.01 (m, 2H,
OCH2), 4.08 (dd, 2H, J =11.0, 4.8 Hz, H-5), 4.10–4.35 (m, 4H, H-4, H-5), 5.00 (s,
1.6H, H-1bmaj), 5.04 (s, 0.2H, H-1bmin) 5.15–5.38 (m, 4.2H, H-1a, H-2, H-3), 5.75 (dd,
2H, J =2.9, 2.6 Hz, CH ); 13C (75 MHz, CDCl3) d 20.4 (CH3), 20.5 (CH3), 20.7
(CH3), 64.4 (C-5b), 64.6 (C-5a), 67.3 (OCH2-bmaj), 67.9 (OCH2-bmin), 69.8 (OCH2-a),
71.5 (C-4b), 71.9 (C-4a), 74.6 and 78.5 (C-2a, C-3a), 74.8 and 78.6 (C-2b, C-3b),
102.1 (C-1a), 104.4 (C-1bmaj), 105.3 (C-1bmin), 128.6 ( CH-b), 128.8 ( CH-a), 169.5,
169.6, and 170.6 (CO).
Anal. Calcd for C26H36O16 (604.57): C, 51.66; H, 6.00. Found: C, 51.69; H, 6.17.
(E)-1,4-Bis[2,3,4,6-tetra-O-acetyl-D-glucopyranosyloxy)but-2-ene (3d). Yield:
209 mg (56%) (as a 1:1 mixture of the a,a/a,b anomers); white solid; Rf 0.13 (ethyl

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PALLADIUM-CATALYZED SYNTHESIS
553
1
acetate/petroleum ether 2:3); H NMR (300 MHz, CDCl3) d 2.00 (s, CH3), 2.02 (s,
CH3), 2.08 (s, CH3), 2.09 (s, CH3), 2.16 (s, CH3), 3.65–3.73 (m, H-5b), 3.95–4.35 (m,
OCH2CH, H-5a, H-6), 4.56 (d, 0.5H, J =7.7 Hz, H-1b), 4.89 (dd, 1.5H, J = 3.7, 10.0
Hz, H-2a), 4.95–5.15 (m, H-1a, H-4a, H-2b), 5.23 (dd, 0.5H, J =9.6, 9.6 Hz, H-4b),
5.48 (dd, 0.5H, J =9.9, 9.7 Hz, H-3b), 5.50 (dd, 1.5H, J = 9.7, 9.7 Hz, H-3a), 5.77 (dd,
J = 6.6, 4.0 Hz, CH ), 5.81 (dd, J = 4.0, 4.0 Hz, CH ); 13C (75 MHz, CDCl3) d
20.6 (CH3), 20.7 (CH3), 20.8 (CH3), 61.9 (C-6), 67.6 (OCH2a), 68.6 (OCH2b), 67.4 (C-
5a), 68.5 (C-4b), 68.6 (C-4a), 70.1 (C-3a), 70.7 (C-2a), 71.3 (C-2b), 71.8 (C-5b), 72.8
(C-3b), 94.8 (C-1amin), 95.1 (C-1amaj), 99.7 (C-1b), 127.7 ( CH-b), 128.5 ( CH-a),
129.2 ( CH-a), 169.4, 169.6, 170.0, 170.1, 170.2, and 170.6 (CO).
Anal. Calcd for C32H44O20 (748.12): C, 51.37; H, 5.88. Found: C, 51.45; H, 6.12.
(E)-1,4-Bis[2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranosyloxy)but-
2-ene (3e). Yield: 201 mg (54%) (as a 9:1 mixture of the a,a/a,b anomers); oil; Rf
0.36 (ethyl acetate/petroleum ether/CH3OH 8:1:1); aa anomer (in the mixture) 1H
NMR (500 MHz, CDCl3) d 1.95 (s, 6H, CH3), 2.00 (s, 6H, CH3), 2.01 (s, 6H, CH3),
2.08 (s, 6H, CH3), 3.95 (ddd, 2H, J =9.8, 4.1, 2.3 Hz, H-5), 4.01 (dd, 2H, J =13.0, 3.1
Hz, CH2-CH ), 4.11 (dd, 2H, J = 12.3, 2.3 Hz, H-6), 4.19 (dd, 2H, J =13.0, 2.8 Hz,
CH2-CH ), 4.23 (dd, 2H, J =12.3, 4.1 Hz, H-6), 4.34 (ddd, 2H, J = 10.4, 9.3, 3.5 Hz,
H-2), 4.90 (d, 2H, J = 3.5 Hz, H-1), 5.12 (dd, 2H, J =9.8, 9.8 Hz, H-3), 5.22 (dd, 2H,
J = 10.4, 9.8 Hz, H-4), 5.80 (dd, 2H, J =3.2, 2.8 Hz, CH ), 5.88 (d, 2H, J =9.3 Hz,
NH); 13C (75 MHz, CDCl3) d 19.6 (CH3), 19.7 (CH3), 19.8 (CH3), 22.1 (NHCOCH3),
50.9 (C-2), 60.9 (C-6), 66.7 (OCH2), 66.9 (C-5), 67.2, 70.1 (C-3, C-4), 95.7 (C-1),
1
128.1 ( CH ), 168.3, 169.1, 169.7, and 170.4 (CO); a,b anomer (in the mixture) H
NMR (500 MHz, CDCl3) d 1.93 (s, CH3), 1.96 (s, CH3), 2.00 (s, CH3), 2.05 (s, CH3),
4.86 (d, J =10.0 Hz, H-1b), 4.92 (d, J =3.5 Hz, H-1a), 4.24–4.30 (ddd, J = 9.4, 9.3, 3.5
Hz, H-2a), 5.26 (dd, J = 9.8, 9.5 Hz, H-3a), 5.73–5.76 (m, CH ), 5.94 (d, J =9.5
Hz, NH); 13C (75 MHz, CDCl3) d 19.7 (CH3), 20.1 (CH3), 22.1 (NHCOCH3), 51.3 (C-
2), 61.2 (C-6), 66.7 (OCH2), 66.4, 67.4, 69.9 (C-3, C-4, C-5), 90.6 (C-1a), 95.6 (C-1b),
127.9 ( CH ), 168.4, 169.3, 169.9, and 170.3 (CO).
Anal. Calcd for C32H46O18N2 (746.73): C, 51.47; H, 6.21; N, 3.75. Found: C,
51.22; H, 6.17; N, 3.65.
1,2-Bis[3-(2,3;5,6-di-O-isopropylidene- -D-mannofuranosyloxy)-(E)-propenyl]-
benzene (8b). Yield: 128 mg (38%); oil; Rf 0.44 (ethyl acetate/petroleum ether 1:4); 1H
NMR (200 MHz, CDCl3) d 1.33 (s, 6H, CH3), 1.39 (s, 6H, CH3), 1.47 (s, 12H, CH3),
4.00–4.41 (m, 12H, H-4, H-5, H-6, OCH2 CH ), 4.65 (d, 2H, J = 5.9 Hz, H-2), 4.82
(dd, 2H, J =5.9, 3.5 Hz, H-3), 5.1 (s, 2H, H-1), 6.05–6.19 (m, 2H, CH2CH ), 6.87 (d, 2H,
J = 15.7 Hz, CH ), 7.30–7.40 (m, 4H, C6H4); 13C (50 MHz, CDCl3) d 24.6 (CH3),
25.3 (CH3), 26.0 (CH3), 27.0 (CH3), 67.0 (C-6), 68.0 (OCH2), 73.3 (C-5), 79.6 (C-3), 80.5
(C-2, 85.2 (C-4), 105.8 (C-1), 109.3, 112.7, 127.9, 130.7, and 135.0 (C6H4), 126.8
(
CH), 127.7 ( CH).
Anal. Calcd for C36H50O12 (674.79): C, 64.08; H, 7.47. Found: C, 64.25; H, 7.40.
1,2-Bis[3-(2,3,5-tri-O-acetyl-D-ribofuranosyloxy)-(E)-propenyl]benzene
(8c). Yield: 223 mg (63%) (as a 3:1 mixture of the b,b/a,b anomers); oil; Rf 0.61 (ethyl
1
acetate/petroleum ether 2:1); H NMR (300 MHz, CDCl3) d 2.04 (s, CH3min), 2.06 (s,
CH3), 2.07 (s, CH3), 2.11 (s, CH3), 2.13 (s, CH3min), 4.02–4.28 (m, 4H, H-4, H-5), 4.28–

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SINOU ET AL.
4.50 (m, 6H, H-5, OCH2), 5.00 (m, 0.25H, H-2a), 5.11 (bs, 1.75H, H-1b), 5.18 (m, 0.25H,
H-3a), 5.26 (d, 0.25H, J = 4.4 Hz, H-1a), 5.28 (d, 1.75H, J = 4.4 Hz, H-2b), 5.38 (dd,
1.75H, J =6.0, 4.4 Hz, H-3b), 6.11 (dt, 4H, J = 15.8, 6.0 Hz, -CH2CH ), 6.88 (d, 2H,
J =15.8 Hz, CH ), 7.20–7.28 (m, 2H, C6H4), 7.38–7.48 (m, 2H, C6H4); 13C (75 MHz,
CDCl3) d 20.5 (CH3), 20.6 (CH3), 20.8 (CH3), 63.5 (C-5a), 64.4 (C-5b), 68.4 (OCH2a),
68.7 (OCH2b), 69.9 (C-4a), 70.8 (C-3a), 71.6 (C-4b), 74.9 (C-3b), 78.6 (C-2b), 79.3 (C-
2a), 99.6 (C-1a), 104.3 (C-1b), 126.7, 130.7, and 134.9 (C6H4), 127.4, 127.9 ( CH ),
169.6 (CO-b), 169.7 (CO-b), 169.9 (CO-a), 170.6 (CO-b).
Anal. Calcd for C34H44O16 (708.26): C, 57.61; H, 6.26. Found: C, 57.26; H, 5.95.
1,2-Bis[3-(2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranosyloxy)-(E)-
propenyl]benzene (8e). Yield: 250 mg (59%) (as a 7:3 mixture of the a,a/a,b anomers);
yellow solid; Rf 0.51 (ethyl acetate/methanol 8:2:1); 1H NMR (300 MHz, CDCl3) d 1.92
(s, 6H, CH3), 2.00 (s, 6H, CH3), 2.01 (s, 6H, CH3), 2.06 (s, 6H, CH3), 3.90–4.40 (m, 12H,
H-2, H-5, H-6, OCH2), 4.76 (d, 0.3H, J = 9.2 Hz, H-1b), 4.96 (d, 1.7 Hz, J = 3.3 Hz, H-1a),
5.13 (dd, 2H, J =9.9, 9.2 Hz, H-4), 5.24 (dd, 2H, J =10.3, 9.9 Hz, H-3), 5.91 (d, 2H, J =9.6
Hz, NH), 6.12 (dt, 2H, J = 15.4, 6.5 Hz, -CH2 CH ), 6.87 (d, 2H, J =15.4 Hz, CH ),
7.26 (dd, 2H, J =5.1, 3.3 Hz, C6H4), 7.42 (d, 2H, J = 3.3 Hz, C6H4); 13C NMR (75 MHz,
CDCl3) d 20.6 (CH3), 20.7 (2 Â CH3), 23.1 (CH3), 51.9 (C-2a), 52.3 (C-2b), 62.1 (C-6),
67.4 (C-5b), 68.0, 68.3, and 71.2 (C-3, C-4, C-5), 68.8 (OCH2CH ), 91.5 (C-1b), 96.6
(C-1a), 127.1, and 131.5 ( CH ), 126.8, 128.3, and 134.6 (C6H4), 169.3 (CO-a), 170.2
(CO-a), 170.3 (CO-b), 170.7 (CO-a), 170.9 (CO-b), 171.4 (CO-a).
Anal. Calcd for C40H52O18N2 (848.86): C, 56.60; H, 6.17. Found: C, 56.70; H, 6.17.
Hydrogenation of compounds 3 and 8. A solution of the unsaturated bis-
saccharide 3 or 8 (0.11 mmol) in ethyl acetate (15 mL) was stirred under a hydrogen
atmosphere at room temperature in the presence of Pd/C 10% (9 mg) for 24 h. The
solvent was evaporated, and the residue was purified by column chromatography on
silica gel to give the saturated bis-saccharide 4 or 9.
1,4-Bis-O-(1,2;5,6-di-O-isopropylidene- -D-glucofuranosid-3-yl)butanediol
25
(4a). Yield: 63 mg (100%); oil; Rf 0.28 (petroleum ether/ethyl acetate 3:1); [a]D À 33.5
(c 0.8, CHCl3); 1H NMR (300 MHz, CDCl3) d 1.32 (s, 6H, CH3), 1.34 (s, 6H, CH3), 1.42
(s, 6H, CH3), 1.50 (s, 6H, CH3), 1.55–1.70 (m, 4H, CH2), 3.45–3.70 (m, 4H, OCH2), 3.85
(d, 2H, J =2.9 Hz, H-3), 3.98 (dd, 2H, J =8.5, 5.9 Hz, H-6), 4.08 (dd, 4H, J = 8.5, 5.9 Hz,
H-6), 4.10 (dd, 2H, J =7.5, 2.9 Hz, H-4), 4.29 (ddd, 2H, J = 7.5, 5.9, 5.9 Hz, H-5), 4.52 (d,
2H, J = 3.7 Hz, H-2), 5.86 (d, 2H, J = 3.7 Hz, H-1); 13C (50 MHz, CDCl3) d 25.4 (CH3),
26.3 (CH3), 26.8 (CH2), 26.8 (CH3), 67.3 (C-6), 70.2 (OCH2), 72.5 (C-5), 81.2 and 82.1
(C-3, C-4), 82.6 (C-2), 105.2 (C-1), 108.9 (CMe2), 111.8 (CMe2).
Anal. Calcd for C28H46O12 (574.67): C, 58.52; H, 8.07. Found: C, 58.58; H, 8.15.
1,4-Bis(2,3;5,6-di-O-isopropylidene- -D-mannofuranosyloxy)butane (4b).
Yield: 63 mg (100%); oil; Rf 0.38 (petroleum ether/ethyl acetate 3:1); [a]D25 + 51.7
1
(c 0.8, CHCl3); H NMR (300 MHz, CDCl3) d 1.33 (s, 6H, CH3), 1.38 (s, 6H, CH3),
1.46 (s, 6H, CH3), 1.47 (s, 6H, CH3), 1.57–1.63 (m, 4H, CH2), 3.34–3.42 (m, 2H,
OCH2), 3.59–3.67 (m, 2H, OCH2), 3.91 (dd, 2H, J = 7.7, 3.6 Hz, H-4), 4.03 (dd, 2H,
J =8.7, 4.4 Hz, H-6), 4.12 (dd, 2H, J = 8.7, 6.2 Hz, H-6), 4.40 (ddd, 2H, J = 7.7, 6.2, 4.4

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PALLADIUM-CATALYZED SYNTHESIS
555
Hz, H-5), 4.58 (d, 2H, J =5.9 Hz, H-2), 4.78 (dd, 2H, J =5.9, 3.6 Hz, H-3), 4.97 (s, 2H,
H-1); 13C (50 MHz, CDCl3) d 24.5 (CH3), 25.2 (CH3), 25.9 (CH3), 26.1 (CH2), 66.9
(OCH2), 67.0 (C-6), 73.2 (C-5), 79.5 and 80.4 (C-2, C-3), 85.1 (C-4), 106.3 (C-1),
109.2 (CMe2), 112.6 (CMe2).
Anal. Calcd for C28H46O12 (574.67): C, 58.52; H, 8.07. Found: C, 58.73; H, 8.17.
1,4-Bis(2,3,5-tri-O-acetyl-D-ribofuranosyloxy)butane (4c). Yield: 66 mg
(100%) (as a 1:4 mixture of the a,b/b,b anomers); oil; Rf 0.51 (ethyl acetate/petroleum
1
ether 2:1); H NMR (300 MHz, CDCl3) d 1.55–1.63 (m, 4H, CH2), 2.02 (s, 6H, CH3),
2.06 (s, 6H, CH3), 2.08 (s, 6H, CH3), 3.30–3.45 (m, 2H, OCH2), 3.60–3.80 (m, 2H,
OCH2), 4.03–4.15 (m, 2H, H-4), 4.20–4.35 (m, 4H, H-5), 4.75–4.95 (m, 0.2H, H-2a),
4.96 (s, 1.60H, H-1bmaj), 4.99 (s, 0.2H, H-1bmin), 5.19 (bd, 1.8H, J =4.4 Hz, H-2b),
5.23 (d, 0.2H, J= 5.9 Hz, H-1a), 5.29 (dd, 2H, J = 7.6, 4.4 Hz, H-3), ); 13C (75 MHz,
CDCl3) d 20.5 (CH3), 20.6 (CH3), 20.8 (CH3), 23.9 (CH2a), 26.1 (CH2-b), 63.2 (C-5a),
64.7 (C-5b), 67.9 (OCH2-b), 69.5 (OCH2a), 71.5 (C-4a), 71.6 (C-4b), 74.7 and 75.0
(C-2a, C-3a), 74.8 and 78.4 (C-2b, C-3b), 104.9 (C-1amin), 105.2 (C-1bmaj), 105.4 (C-
1bmin), 169.6, 169.7, and 170.5 (CO).
Anal. Calcd for C26H38O16 (606.58): C, 51.48; H, 6.31. Found: C, 51.35; H, 6.48.
1,4-Bis[2,3,4,6-tetra-O-acetyl-D-glucopyranosyloxy)butane (4d). Yield: 82 mg
(100%) (as a 1:1 mixture of the a,a/a,b anomers); oil; Rf 0.13 (ethyl acetate/petroleum
1
ether 3:2); H NMR (300 MHz, CDCl3) d 1.55–1.80 (m, 4H, CH2), 1.98 (s, CH3), 1.99
(s, CH3), 2.00 (s, CH3), 2.01 (s, CH3), 2.02 (s, CH3), 2.04 (s, CH3), 2.06 (s, CH3), 2.07
(s, CH3), 3.35–3.45 (m, 2H, OCH2), 3.65–3.75 (m, 2H, OCH2), 3.95–4.25 (m, 6H, H-
5, H-6), 4.49 (d, 0.5H, J =7.4 Hz, H-1b), 4.84 (dd, 1.5H, J =10.3, 3.7 Hz, H-2a), 4.93–
5.10 (m, H-4, H-2b, H-1a), 5.19 (dd, 0.5H, J = 9.5, 8.8 Hz, H-3b), 5.43 (dd, 1H, J =9.5,
9.6 Hz, H-3amaj), 5.44 (dd, 0.5H, J =10.3, 9.6 Hz, H-3amin); 13C (75 MHz, CDCl3) d
20.5 (CH3), 20.6 (2 Â CH3), 20.7 (CH3), 25.8 (CH2min), 26.1 (CH2), 26.2 (CH2min), 61.9
(C-6), 67.2 (C-5a), 68.2, 68.3 and 69.5 (OCH2), 68.4 (C-4b), 68.6 (C-4a), 70.1 (C-3a),
70.9 (C-2a), 71.3 (C-2b), 71.7 (C-5b), 72.8 (C-3b), 95.7 (C-1a), 95.8 (C-1a), 100.7 (C-
1b), 169.2, 169.5, 169.4, 170.1, 170.2, and 170.6 (CO).
Anal. Calcd for C32H46O20 (750.12): C, 51.23; H, 6.13. Found: C, 51.10; H, 6.19.
1,4-Bis[2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranosyloxy)butane
(4e). Yield: 82 mg (100%) (as a 9:1 mixture of the a,a/a,b anomers); oil; Rf 0.36
1
(ethyl acetate/petroleum ether/CH3OH 8:1:1); anomer a,a (in the mixture) H NMR
(300 MHz, CDCl3) d 1.50–1.80 (m, 4H, CH2), 1.91 (s, 6H, CH3), 1.96 (s, 6H, CH3),
1.97 (s, 6H, CH3), 2.03 (s, 6H, CH3), 3.40–3.50 (m, 2H, OCH2), 3.63–3.74 (m, 2H,
OCH2), 3.92 (ddd, 2H, J =10.3, 4.4, 2.3 Hz, H-5), 4.07 (dd, 2H, J =12.2, 2.3 Hz, H-6),
4.23 (dd, 2H, J =12.2, 4.5 Hz, H-6), 4.34 (ddd, 2H, J = 10.3, 8.8, 3.7 Hz, H-2), 4.87 (d,
2H, J = 3.7 Hz, H-1), 5.09 (dd, 2H, J =9.5, 9.5 Hz, H-4), 5.19 (dd, 2H, J = 10.3, 10.3
Hz, H-3), 5.90 (d, 2H, J = 8.8 Hz, NH); 13C (75 MHz, CDCl3) d 20.6 (CH3), 20.7
(2 Â CH3), 23.0 (NHCOCH3), 26.0 (CH2), 52.0 (C-2), 62.1 (C-6), 67.8, 68.4 and 71.1
(C-3, C-4, C-5), 67.8 (OCH2), 97.0 (C-1), 169.3, 170.1, 170.6, and 171.4 (CO); signals
1
corresponding to the anomer a,b (in the mixture): H NMR (300 MHz, CDCl3) d 1.90,
1.96, 2.02 (CH3), 4.77 (d, J = 9.2 Hz, H-1b), 4.82 (d, J =3.7 Hz, H-1a); 13C (75 MHz,
CDCl3) d 52.6 (C-2), 91.9 (C-1), 170.2 (CO).

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SINOU ET AL.
Anal. Calcd for C32H46O18N2 (746.73): C, 51.47; H, 6.21; N, 3.75. Found: C,
51.22; H, 6.17; N, 3.65.
1,2-Bis[3-(2,3,5-tri-O-acetyl-D-ribofuranosyloxy)propyl]benzene (9c). Yield:
78 mg (100%) (as a 7:3 mixture of the b,b/a,b anomers); oil; Rf 0.61 (ethyl acetate/
petroleum ether 2:1); 1H NMR (300 MHz, CDCl3) d 1.78–1.90 (m, 4H, CH2), 2.05 (s, 6H,
CH3), 2.06 (s, 6H, CH3), 2.10 (s, 6H, CH3), 2.66 (t, 4H, J =7.5 Hz, CH2), 3.42 (dt, 2H,
J =9.2, 6.6 Hz, OCH2), 3.76 (dt, 2H, J = 9.2, 5.9 Hz, OCH2), 4.11 (dd, 2H, J = 11.4, 5.5 Hz,
H-5), 4.22–4.40 (m, 4H, H-4, H-5), 4.95–5.05 (bs, 1.7H, H-1b), 5.17 (dd, 0.3H, J =7.4,
4.4 Hz, H-2a), 5.20–5.30 (m, 0.6H, H-3a, H-1a), 5.23 (d, 0.3H, J =4.4 Hz, H-2b), 5.33
(dd, 2H, J =6.6, 4.4 Hz, H-3), 7.10–7.15 (m, 4H, C6H4); 13C (75 MHz, CDCl3) d 20.5
(CH3), 20.6 (CH3), 20.8 (CH3), 28.8 (CH2), 30;7 (CH2), 63.5 (C-5a), 64.7 (C-5b), 67.6
(OCH2b), 68.0 (OCH2a), 70.0 (C-4a), 70.8 (C-3a), 71.7 (C-4b), 74.8 (C-3b), 78.4 (C-2b),
78.9 (C-2a), 100.6 (C-1a), 105.3 (C-1b), 126.2, 129.3, and 139.3 (C6H4), 169.6, 169.7,
and 170.6 (CO).
Anal. Calcd for C34H48O16 (712.75): C, 57.28; H, 6.79. Found: C, 57.39; H, 6.40.
1,2-Bis[3-(2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranosyloxy)pro-
pyl]benzene (9e). Yield: 94 mg (100%) (as a 7:3 mixture of the a,a/a,b anomers);
white solid; Rf 0.51 (ethyl acetate/petroleum ether/methanol 8:2:1); 1H NMR (300
MHz, CDCl3) d 1.75–1.90 (m, 4H, CH2), 1.93 (s, 6H, CH3), 2.00 (s, 6H, CH3),
2.02 (s, 6H, CH3), 2.03 (s, 6H, CH3), 2.60–2.80 (m, 4H, CH2), 3.50 (dt, 2H, J =
10.0, 6.6 Hz, OCH2CH2), 3.71 (dt, 2H, J =10.0, 6.6 Hz, OCH2CH2), 3.86 (ddd, 2H,
J =9.5, 4.5, 2.2 Hz, H-5), 4.02 (dd, 2H, J = 12.5, 2.2, Hz, H-6), 4.17 (dd, 2H,
J =12.5, 4.5 Hz, H-6), 4.31 (ddd, 2H, J =9.5, 9.3, 3.3 Hz, H-2), 4.70 (d, J =9.2 Hz,
0.3H, H-1b), 4.84 (d, J =3.3 Hz, 1.7H, H-1a), 5.09 (dd, 2H, J =9.5, 9.5 Hz, H-4),
5.22 (dd, 2H, J = 9.5, 9.5 Hz, H-3), 5.89 (d, 2H, J = 9.2 Hz, NH), 7.00–7.20 (m, 4H,
C6H4); 13C (75 MHz, CDCl3) d 20.6 (CH3), 20.7 (2 Â CH3), 20.8 (CH3), 23.1 (CH3a),
23.2 (CH3b), 25.6 (2 Â CH2), 28.9 (CH2C6H4), 30.3 (CH2C6H4), 51.9 (C-2a), 52.3 (C-
2b), 61.9 (C-6), 67.7, 68.3, and 71.2 (C-3, C-4, C-5), 67.9 (OCH2a), 67.8 (OCH2b),
93.4 (C-1b), 97.3 (C-1a), 126.5, 129.2, and 138.8 (C6H4), 169.3, 170.0, 170.6, and
171.4 (CO).
Anal. Calcd for C40H56O18N2 (852.89): C, 56.33; H, 6.62. Found: C, 56.82; H, 6.35.
ACKNOWLEDGMENT
One of us (A. Z.) thanks Region Rhoˆne-Alpes for a fellowship.
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Received April 29, 2002
Accepted August 29, 2002