Synthesis of two heptasaccharide analogues of the lentinan repeating unit

Article abstract of DOI:10.1016/j.carres.2003.08.003

β-D-Glcp-(1→3)-β-D-Glcp-(1→3)-β-D-Glcp-(1→3) -β-D-Glcp-(1→3)-[β-D-Glcp-(1→3)-β-D-Glcp-(1→6)] -β-D-Glcp (18) and the allyl glycoside of β-D-Glcp-(1→3)-[β- D-Glcp-(1→6)]-β-D-Glcp-(1→3)-β-D-Glcp-(1→3) -β-D-Glcp-(1→3)[-β-D-Glcp-(1→6)]-α-D-Glcp (29) were synthesized as the analogues of the lentinan repeating heptaose by building the pentasaccharide backbones first, followed by attaching the side chains. 4,6-O-Benzylidenated mono-13 or disaccharide 8 were used as the acceptor to ensure the β linkage in the synthesis of 18, while 4,6-O-benzylidenated disaccharides 21 and 23 were used as the donor and acceptor, respectively, to ensure the β linkage in the synthesis of 29.

Full text of DOI:10.1016/j.carres.2003.08.003

Carbohydrate Research 338 (2003) 2813ꢀ2823
/
www.elsevier.com/locate/carres
Synthesis of two heptasaccharide analogues of the lentinan repeating
unit
Wei Zhao, Guangbin Yang, Fanzuo Kong*
Research Center for Eco-Environmental Sciences, Academia Sinica, P.O. Box 2871, Beijing 100085, PR China
Received 18 July 2003; accepted 11 August 2003
Abstract
b-
the allyl glycoside of b-
a- -Glcp (29) were synthesized as the analogues of the lentinan repeating heptaose by building the pentasaccharide backbones first,
D
-Glcp-(10
/
3)-b-D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-[b-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
6)]-b-
D
-Glcp (18) and
D
-Glcp-(10
/
3)-[b-
D
-Glcp-(10
/
6)]-b-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)[-b-
D
-Glcp-(106)]-
/
D
followed by attaching the side chains. 4,6-O-Benzylidenated mono-13 or disaccharide 8 were used as the acceptor to ensure the b
linkage in the synthesis of 18, while 4,6-O-benzylidenated disaccharides 21 and 23 were used as the donor and acceptor, respectively,
to ensure the b linkage in the synthesis of 29.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: Oligosaccharide; Glucose; Synthesis
1. Introduction
lentinan consists of a glucoheptaose repeating unit3 as
shown in Fig. 1. Its synthesis has been reported by our
group.5
Bioassay showed that at a dose of 5 mg/kg, the
synthetic allyl glucoheptaoside inhibited U14 tumor
effectively (58.4%).6 Encouraged by the bioassay results,
we are trying to synthesize more structurally diverse 3,6-
Obtained from Lentinus edodes, an edible mushroom
popular in East Asia, lentinan is a glucan that is well
known as an antitumor agent1 and immunostimulant in
Japan and China. In a very small dosage, lentinan has
marked antitumor effects in syngeneic and autochto-
nous hosts. Clinically, lentinan has proved effective with
chemotherapeutic agents for patients with recurrent
gastric and colorectal cancer.2 Some physicochemical
and immunopharmacological investigations have shown
that the antitumor activity of these glucans may be
branched glucans and investigate structureꢀ
relationships. We present herein the syntheses of a
glucoheptaose 18 consisting of a b-(103)-linked pen-
taose backbone with a b-(103)-linked biose side chain
/activity
/
/
attached at C-6 of the backbone, and a glucoheptaose 29
consisting of the same pentaose backbone with glucosyl
side chains linked at C-6 and C-6§of the backbone.
related to the tripletꢀ
/
helix structures of the b-(10
/3)-
linked backbone chains,3a,3b and some biological aspects
of these b-glucans have been reported.3c,3d,3e It was also
reported that only higher molecular-weight fractions
2. Results and discussion
(MWꢀ16,000) obtained from partial hydrolysis of
/
lentinan with formic acid showed antitumor activity.4
We hypothesize that the activity of lentinan is dependent
upon its basic structural oligosaccharide unit rather than
its macroscopic morphology. The major structure of
Scheme 1 shows the synthesis of the glucoheptaose 18.
1,2:5,6-Di-O-isopropylidene-a-
used as the starting material. Allylation of 1 gave 2,
subsequent hydrolysis in 80% HOAcꢀH2O removed the
D-glucofuranose (1) was
/
two isopropylidene groups resulting in ring expansion at
the same time. Benzoylation of the hemiacetal with
benzoyl chloride in pyridine, followed by 1-O-selective
debenzoylation and trichloroacetimidation,7 afforded
* Corresponding author. Tel.: ꢁ
10-62923563.
E-mail address: fzkong@mail.rcees.ac.cn (F. Kong).
/
86-10-62936613; fax: ꢁ86-
/
0008-6215/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2003.08.003

2814
W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ2823
/
hemiacetal 20, and subsequent trichloroacetimidation
afforded the disaccharide 21. Meanwhile, the trisacchar-
ide acceptor 25 was obtained by coupling 4,6-di-O-
acetyl-2-O-benzoyl-3-O-chloroacetyl-a-D-glucopyrano-
syl trichloroacetimidate (22)5 with the disaccharide
acceptor 23, followed by dechloroacetylation with
thiourea. The benzylidene group in 23, played a key
role leading the coupling to b linkage, although it was at
the reducing end of the disaccharide acceptor. Here, a
remote control of the benzylidene group for the stereo-
selective glucosylation was shown, as it was known8 that
a linkage was always obtained when the benzylidene
group was replaced with acyl groups for the similar
couplings. Condensation of 25 with 21 was carried out
readily giving b-linked pentasaccharide 26, and the b-
stereoselectivity of this reaction was also controlled by
the benzylidene group in the donor 21 and also maybe in
the acceptor 25. Otherwise, if benzylidene groups were
replaced by acyl groups, a-linked pentasaccharides
would be the products.8 Removal of the benzylidene
Fig. 1. Structure of lentinan.
one donor 3. Meanwhile, 2 was transformed to another
donor 4 through hydrolysis, 4,6-O-benzylidenation,
benzoylation, 1-O-selective debenzoylation, and tri-
chloroacetimidation. The two donors 3 and 4 were key
synthons in the present research, since the required
disaccharide building blocks and related tetrasaccharide
were readily obtained from them. Thus, condensation of
3 with 1 gave the b-(10
/
3)-linked disaccahride 5, and
subsequent hydrolysis, acetylation, selective 1-O-deace-
tylation, and trichloroacetimidation afforded the dis-
accharide donor 6. Meanwhile, coupling of 4 with 1
furnished the b-(10
deallylation gave the disaccharide acceptor 8. Coupling
of 8 with 6 gained the b-(103)-linked tetrasaccharide 9
/
3)-linked disaccharide 7, whose
groups with toluenesulfonic acid in acetonitrileꢀethyl-
/
/
ene glycol (75%), followed by coupling with perbenzoyl-
ated glucosyl trichloroacetimidate gave the 6-, 6§-
branched heptaoside 28 (68%). Finally, deacylation of
28 in ammonia-saturated methanol yielded the target
compound. The 1H and 13C NMR spectra showed all of
the characteristic signals, such as at d 4.98 with J1,2 3.6
Hz for a H-1, 4.76, 4.76, 4.75, 4.53, 4.50, and 4.50 with J
8.0 Hz for b H-1, d 102.6, 102.5, 102.5, 102.3, 102.3,
102.3 for b C-1, and 97.03 for a C-1. The four
glycosylated C-3 signals at d 84.53, 83.94, 83.80, 81.89
also confirmed the selective 6-glycosylation of 27;
otherwise, if C-4 were glycosylated, additional signals
in good yield (85.5%), and no a-linked product was
detected. The benzylidene group in 8 played an im-
portant role leading the coupling to b linkage. Other-
wise, if acetylated or benzoylated disaccharide acceptors
were used to couple with acylated disaccharide donors,
a-linked products were always obtained.8 The tetra-
saccharide 9 was transformed to the tetrasaccharide
donor 12 by hydrolysis, acetylation, selective 1-O-
deacetylation, and trichloroacetimidation. An attempt
to couple 12 with 1 or 8 was not successful, giving a poor
yield. However, condensation of 12 with allyl 2-O-
benzoyl-4,6-O-benzylidene-a-
D
-glucopyranoside (13)5
at d ꢁ/80 would have appeared.
gave the required b-linked pentasaccharide in good
yield (85.5%). Debenzylidenation of 14 went smoothly
to afford the pentasaccharide acceptor 15, and subse-
quent selective C-6 glycosylation of 15 with the dis-
accharide donor 16 yielded protected heptasaccharide
17. Finally, deallylation and deacylation of 17 furnished
the target heptasaccharide 18. Compound 18 was
3. Experimental
3.1. General methods
Melting points were determined with a ‘Mel-Temp’
apparatus. Optical rotations were determined with a
1
characterized by H and 13C NMR spectrometry show-
ing signals at d 4.73ꢀ
/
4.66 with J1,2 7.8ꢀ
/
8.0 Hz for seven
PerkinꢀElmer model 241-MC automatic polarimeter for
/
1
b H-1, and d 102.4, 102.4, 102.3, 102.3, 102.2, 102.2,
102.1 for seven b C-1. The signal at d 67.7 for C-6
proved the 6-glycosylation of 15. The lack of signals in
solutions in a 1-dm, jacketed cell. H and 13C NMR
spectra were recorded with Varian XL-400 spectro-
meters, for solutions in CDCl3 or in D2O as indicated.
Individual resonances could not be identified with the
specific sugar residues. Chemical shifts are expressed in
ppm downfield from the Me4Si absorption. Mass
spectra were recorded with a VG PLATFORM mass
spectrometer using the ESI mode. Thin layer chromato-
graphy (TLC) was performed on silica gel HF with
detection by charring with 30% (v/v) sulfuric acid in
MeOH or by UV detection. Column chromatography
the region of d 76ꢀ
glycosylation; otherwise, if C-4 were glycosylated, a
signal at d ꢁ80 ppm would have appeared.
Scheme 2 shows the synthesis of another glucohep-
taose 29. First, a b-(103)-linked disaccharide 19 was
/
82 also confirmed the selective 6-
/
/
obtained by coupling of perbenzoylated glucosyl tri-
chloroacetimidate with the acceptor 13. Owing to the
use of benzylidenated acceptor, no a-linked product was
detected. Deallylation of 19 with PdCl2 in 90% acetic
acid containing sodium acetate smoothly furnished the
was conducted by elution of a column (8ꢂ
/
100, 16ꢂ
/
240, 18ꢂ300, 35ꢂ400 mm) of silica gel (100ꢀ
/
/
/
200

W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ
/2823
2815
Scheme 1. (a) AllBr, DMF; (b) i. 80% HOAc, reflux, 3ꢀ
Cl3CCN, CH2Cl2, rt, overnight; (c) i. 80% HOAc, reflux, 3ꢀ
MeOH, rt, ꢁ10 h; v. K2CO3, Cl3CCN, CH2Cl2, rt, overnight; (d) TMSOTf, CH2Cl2, ꢃ
4 h; ii. Ac2Oꢀpyridine; iii. NH3ꢀtolueneꢀMeOH, rt, 40 min; iv. K2CO3, Cl3CCN, CH2Cl2, rt, overnight; (f) PdCl2, MeOH, rt, 4 h;
(g) NH3ꢀtolueneꢀMeOH, rt, 40 min; (h) CCl3CN, DBU, CH2Cl2 8 h; (i) saturated NH3ꢀMeOH, rt, 72 h.
/
4 h; ii. BzClꢀ
4 h; ii. TsOH, DMF, HC(OEt)3; iii. BzClꢀ
20 8C to rt, 3 h; (e) i. 80% HOAc, reflux, 3ꢀ
/
pyridine; iii. NH3ꢀ
/
tolueneꢀ
/
MeOH, rt, ꢁ
/
10 h; iv. K2CO3,
/
/
pyridine; iv. NH3ꢀ
/
tolueneꢀ
/
/
/
/
/
/
/
/
/
/

2816
W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ2823
/
mesh) with EtOAcꢀ
/
petroleum ether (bp 60ꢀ
/
90 8C) as
TsOH (1.6 g) and HC(OEt)3 (30 mL) were added. The
reaction mixture was stirred for 10 h, at the end of which
the eluent. Analytical LC was performed with a Gilson
high performance ion chromatography (HPLC) consist-
ing of a pump (model 306), stainless steel column
time TLC (2:1 petroleum etherꢀEtOAc) indicated that
/
the reaction was complete. The mixture was concen-
trated, the residue was dissolved in pyridine (100 mL),
and BzCl (40 mL) was added. The reaction mixture was
stirred for 10 h, at the end of which time TLC (3:1
packed with silica gel (Spherisorb SiO2, 10ꢂ
4.6ꢂ250 mm), differential refractometer (132-RI De-
tector), UVꢀVis detector (model 118). EtOAcꢀpetro-
leum ether (bp 60ꢀ90 8C) was used as the eluent at a
flow rate of 1ꢀ4 mL/min. Solutions were concentrated
at a temperature B60 8C under diminished pressure.
/300 or
/
/
/
/
petroleum etherꢀ
complete. The mixture was concentrated and the residue
was dissolved in satd 200:60 NH3ꢀtolueneꢀMeOH (260
mL). The reaction mixture was stirred for 10 h, at the
end of which time TLC (2:1 petroleum etherꢀEtOAc)
indicated that the reaction was complete. The crude 3-
O-allyl-2-O-benzoyl-4,6-O-benzylidene- -glucopyran-
/EtOAc) indicated that the reaction was
/
/
/
/
3.2. 3-O-Allyl-2,4,6-tri-O-benzoyl-a-
trichloroacetimidate (3)
D-glucopyranosyl
/
D
3-O-Allyl-1,2:5,6-di-O-isopropylidene-a-
ose (2) (6.5 g, 0.02 mol) was added to 80% HOAcꢀ
(150 mL). The reaction mixture was refluxed for 3ꢀ
at the end of which time TLC (1:1 petroleum etherꢀ
D
-glucofuran-
H2O
4 h,
ose (8.30 g, 20.2 mmol) was dissolved in CH2Cl2 (50
mL), then CCl3CN (2.0 mL, 40 mmol) and K2CO3 (4.0
g, 30.0 mmol) were added. The reaction mixture was
stirred for 10 h, at the end of which time TLC (3:1
/
/
/
EtOAc) indicated that the reaction was complete. The
mixture was concentrated, the residue was dissolved in
Py, and BzCl (20 mL) was added. The reaction mixture
was stirred for 10 h, at the end of which time TLC (3:1
petroleum etherꢀEtOAc) indicated that the reaction was
complete. The mixture was filtered, and the filtrate was
concentrated. The residue was purified by flash chro-
/
matography (3:1 petroleum etherꢀ
g, 87.1%) as a syrup: [a]D 258 (c 1. 0, CHCl3); H
NMR (400 MHz, CDCl3): d 8.60 (s, 1 H, CNHCCl3),
8.09ꢀ7.40 (m, 10 H, PhH), 6.67 (d, 1H, J1,2 3.6 Hz, H-
1), 5.87ꢀ5.84 (m, 1 H, CH2ÄCHÃ CH2), 5.66 (s, 1 H,
PhCH), 5.38 (dd, 1 H, J2,3 9.6 Hz, H-2), 5.28ꢀ5.20 (m, 1
H, CH2ÄCHÃCH2), 5.13ꢀ5.09 (m, 1 H, CH2ÄCHÃ
CH2O), 4.47ꢀ3.81(m, 7 H, H-3, H-4, H-5, H-6, H-6?,
CH2ÄCHÃCH2). Anal. Calcd for C25H24Cl3NO7: C,
53.86; H, 4.31. Found: C, 53.98; H, 4.19.
/
EtOAc) to give 4 (9.6
1
petroleum etherꢀ
complete. The mixture was concentrated, and the
residue was dissolved in 100:30 satd NH3ꢀtolueneꢀ
/
EtOAc) indicated that the reaction was
ꢁ
/
/
/
/
MeOH (130 mL). The reaction mixture was stirred for
10 h, at the end of which time TLC (2:1 petroleum
/
/
/
/
etherꢀ
/
EtOAc) indicated that the reaction was complete.
-glucopyra-
/
/
/
/
/
The crude 3-O-allyl-2,4,6-tri-O-benzoyl-
D
/
nose (5.3 g, 10 mmol) thus obtained was dissolved in
CH2Cl2 (50 mL), then CCl3CN (1.0 mL, 20 mmol) and
K2CO3 (2.0 g, 15.0 mmol) were added. The reaction
mixture was stirred for 10 h, at the end of which time
/
/
TLC (3:1 petroleum etherꢀ
reaction was complete. The mixture was filtered, and the
filtrate was concentrated. The residue was purified by
/
EtOAc) indicated that the
3.4. 3-O-Allyl-2,4,6-tri-O-benzoyl-b-D-glucopyranosyl-
D-glucofuranose (5)
(103)-1,2:5,6-di-O-isopropylidene-a-
/
flash chromatography (3:1 petroleum etherꢀ
give 3 (5.60 g, 82.1%) as a syrup: [a]D 118 (c 0.5,
CHCl3); H NMR (400 MHz, CDCl3): d 8.60 (s, 1 H,
CNHCCl3), 8.11ꢀ7.35 (m, 15 H, PhH), 6.73 (d, 1 H, J1,2
3.6 Hz, H-1), 5.70ꢀ5.57 (m, 1 H, CH2ÄCH ÃCH2), 5.64
(dd, 1 H, J4,5 J3,4 9.2 Hz, H-4), 5.47 (dd, 1 H, J2,3
9.4 Hz, H-2), 5.11ꢀ4.96 (m, 2 H, CH2ÄCHÃCH2), 4.64ꢀ
/
EtOAc) to
3-O-Allyl-2,4,6-tri-O-benzoyl-b-
chloroacetimidate (3) (7.0 g, 10.3 mmol) and 1,2:5,6-
-glucofuranose (1) (2.95 g, 11.3
mmol) were dried together under high vacuum for 2 h,
then dissolved in anhyd CH2Cl2 (50.0 mL). Me3SiOTf
D-glucopyranosyl tri-
ꢁ
/
1
di-O-isopropylidene-a-
D
/
/
/
/
ꢄ
/
ꢄ
/
(20.0 mL, 0.174 mmol) was added dropwise at ꢃ20 8C
/
/
/
/
/
with N2 protection. The reaction mixture was stirred for
3 h, during which time the temperature was gradually
raised to ambient temperature. Then the mixture was
neutralized with Et3N. Concentration of the reaction
mixture, followed by purification of the product on a
4.13 (m, 6 H). Anal. Calcd for C32H28Cl3NO9: C, 56.72;
H, 4.14. Found: C, 56.80; H, 4.10.
3.3. 3-O-Allyl-2-O-benzoyl-4,6-O-benzylidene-a-D-
glucopyranosyl trichloroacetimidate (4)
silica gel column with 3:1 petroleum etherꢀ
/
EtOAc as the
158 (c
1.0, CHCl3); H NMR (CDCl3, 400 MHz): d 8.09ꢀ7.38
(m, 15 H, 3 PhH), 5.60ꢀ5.52 (m, 1 H, CH2ÄCHCH2),
5.52 (dd, 1 H, J3,4 J4,5 9.3 Hz, H-4?), 5.45 (d, 1 H,
J1,2 3.7 Hz, H-1), 5.30 (dd, 1 H, J1,2 7.8 Hz, J2,3 9.2 Hz,
H-2?), 5.10ꢀ4.91 (m, 2 H, CH2ÄCHCH2), 4.80 (d, 1 H,
H-1?), 4.60 (dd, 1 H, J5,6 5.1, J6,6? 12.0 Hz, H-6?) 4.45ꢀ
3.93 (m, 11 H), 1.40, 1.35, 1.23, 1.11 (4 s, 12 H, CH3).
eluent gave 5 (6.77 g, 85.3%) as a syrup: [a]D
ꢁ
/
1
3-O-Allyl-1,2:5,6-di-O-isopropylidene-a-
ose (2) (13.0 g, 40 mmol) was added to 80% HOAcꢀ
(300 mL). The reaction mixture was refluxed for 3ꢀ
at the end of which time TLC (1:1 petroleum etherꢀ
D
-glucofuran-
H2O
4 h,
/
/
/
/
/
ꢄ
/
ꢄ
/
/
EtOAc) indicated that the reaction was complete. The
mixture was concentrated, the residue was dissolved in
DMF (140 mL), and PhCHO (50 mL, 0.12 mol), p-
/
/
/

W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ
/2823
2817
Scheme 2. PdCl2, HOAcꢀ
thiurea, CH2Cl2ꢀMeOH, reflux, overnight; (e) p-TsOH×
72 h.
/
NaOAc, rt, overnight; (b) CCl3CN, DBU, CH2Cl2, 2 h; (c) TMSOTf, CH2Cl2, ꢃ
/
10 8C, 2ꢀ
/
4 h; (d)
/
/
H2O, ethylene glycol, CH3CN, rt, overnight; (f) saturated NH3ꢀMeOH, rt,
/
Anal. Calcd for C42H46O14: C, 65.12; H, 5.94. Found: C,
65.30; H, 5.90.
that the reaction was complete. The mixture was
concentrated, and the residue was dissolved in 80:30
satd NH3ꢀ
mixture was stirred for 40 min, at the end of which
time TLC (2:1 petroleum etherꢀEtOAc) indicated that
the reaction was complete. The mixture was concen-
trated to dryness. The residue was dissolved in CH2Cl2
(60 mL), and CCl3CN (1.0 mL, 10 mmol) and K2CO3
(2.0 g, 15.0 mmol) were added. The reaction mixture was
stirred for 10 h, at the end of which time TLC (2:1
/
tolueneꢀMeOH (110 mL). The reaction
/
3.5. 3-O-Allyl-2,4,6-tri-O-benzoyl-b-
(103)-2,4,6-tri-O-acetyl-a- -glucopyranosyl
trichloroacetimidate (6)
D-glucopyranosyl-
/
/
D
Compound 5 (4.35 g, 9.5 mmol) was added to 80%
HOAcꢀH2O (100 mL). The reaction mixture was
refluxed for 3ꢀ4 h, then concentrated to dryness. The
/
/
petroleum etherꢀEtOAc) indicated that the reaction was
complete. Concentration of the reaction mixture, fol-
lowed by purification on a silica gel column with 2:1
/
residue was dissolved in pyridine (50 mL), and then
Ac2O (30 mL) was added. After stirring the mixture at rt
for 12 h, TLC (2:1 petroleum etherꢀEtOAc) indicated
/

2818
W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ2823
/
petroleum etherꢀ
disaccharide donor 6 (3.10 g, 42% for four steps) as a
/
EtOAc as the eluent, furnished the
3.8. 3-O-Allyl-2,4,6-tri-O-benzoyl-b-
(103)-2,4,6-tri-O-acetyl-b-
O-benzoyl-4,6-O-benzylidene-b-
3)-1,2:5,6-di-O-isopropylidene-a-
D-glucopyranosyl-
/
D
-glucopyranosyl-(10
/
3)-2-
1
syrup: [a]D
CDCl3): d 8.60 (s, 1 H, CNHCCl3), 8.04ꢀ
PhH), 6.42 (d, 1 H, J1,2 3.6 Hz, H-1), 5.60ꢀ
CH2ÄCH ÃCH2), 5.46 (dd, 1 H, J4,5 J3,4
4?), 5.20 (dd, 1 H, J2,3 9.6 Hz, H-2?), 5.16 (dd, 1 H, J3,4
J4,5 9.6 Hz, H-4), 5.03ꢀ4.89 (m, 2 H, CH2ÄCHÃCH2),
4.90 (d, 1 H, J1,2 8.0 Hz, H-1?), 4.88 (dd, 1 H, J2,3 9.6 Hz,
H-2), 4.64ꢀ4.04 (m, 10 H), 2.05, 1.98, 1.85 (3 s, 9 H,
ꢁ
/
558 (c 0.5, CHCl3); H NMR (400 MHz,
7.40 (m, 15 H,
5.51 (m, 1 H,
9.6 Hz, H-
D
-glucopyranosyl-(10
/
/
D
-glucofuranose (9)
/
/
/
ꢄ
/
ꢄ
/
Donor 6 (3.08 g, 3.20 mmol) and acceptor 8 (1.95 g, 3.44
mmol) were dried together under high vacuum for 2 h,
then dissolved in anhyd CH2Cl2 (30.0 mL). Me3SiOTf
ꢄ
/
ꢄ
/
/
/
/
(20.0 mL, 0.174 mmol) was added dropwise at ꢃ20 8C
/
/
with N2 protection. The reaction mixture was stirred for
3 h, during which time the temperature was gradually
raised to ambient temperature. Then the mixture was
neutralized with Et3N. Concentration of the reaction
mixture, followed by purification on a silica gel column
CH3CO). Anal. Calcd for C44H44Cl3NO17: C, 54.72; H,
4.56. Found: C, 54.88; H, 4.59.
3.6. 3-O-Allyl-2-O-benzoyl-4,6-O-benzylidene-b-
glucopyranosyl-(103)-1,2:5,6-di-O-isopropylidene-a-
glucofuranose (7)
D-
/
D-
with 2:1 petroleum etherꢀ
/
EtOAc as the eluent, gave the
468 (c 1.0,
CHCl3); H NMR (400 MHz, CDCl3): d 8.04ꢀ7.30 (m,
25 H, 5 PhH), 5.56ꢀ5.50 (m, 1 H, CH2ÄCHCH2), 5.51
(s, 1 H, PhCH), 5.45 (dd, 1 H, J3,4 J4,5 9.6 Hz, H-
4§), 5.42 (d, 1 H, J1,2 3.6 Hz, H-1), 5.13 (dd, 1 H, J1,2
7.8, J2,3 8.6 Hz, H-2§), 5.07 (dd, 1 H, J1,2 7.9, J2,3
8.8 Hz, H-2?), 5.00ꢀ4.96 (m, 1 H, CH2ÄCHCH2), 4.96
(dd, 1 H, J3,4 J4,5
9.6 Hz, H-4ƒ), 4.90 (dd, 1 H, J1,2
6.1, J2,3 9.0 Hz, H-2ƒ), 4.90ꢀ4.87 (m, 1 H, CH2Ä
product 9 (3.85 g, 85.5%) as a syrup: [a]D
ꢁ
/
1
/
Donor 4 (5.74 g, 10.3 mmol) and acceptor 1 (2.99 g, 11.4
mmol) were dried together under high vacuum for 2 h,
then dissolved in anhyd CH2Cl2 (50.0 mL). Me3SiOTf
/
/
ꢄ
/
ꢄ
/
(20.0 mL, 0.174 mmol) was added dropwise at ꢃ
/
20 8C
ꢄ
/
ꢄ
/
with N2 protection. The reaction mixture was stirred for
3 h, during which time the temperature was gradually
raised to ambient temperature. Then the mixture was
neutralized with Et3N. Concentration of the reaction
mixture, followed by purification on a silica gel column
/
/
ꢄ
/
ꢄ
/
/
/
CHCH2), 4.80 (d, 1 H, J1,2 7.8 Hz, H-1§), 4.70 (d, 1
H, J1,2 7.9 Hz, H-1?), 4.58 (d, 1 H, J1,2 6.1 Hz, H-1ƒ),
with 3:1 petroleum etherꢀ
/
EtOAc as the eluent gave the
24.08 (c 1.0,
CHCl3); H NMR (400 MHz, CDCl3): d 8.10ꢀ7.37 (m,
10 H, 2 PhH), 5.78ꢀ5.69 (m, 1 H, CH2ÄCHCH2), 5.60
(s, 1 H, PhCH), 5.44 (d, 1 H, J1,2 3.7 Hz, H-1), 5.20 (dd,
1 H, J1,2 7.4, J2,3 8.1 Hz, H-2?), 5.20ꢀ5.04 (m, 2 H,
CH2ÄCHCH2), 4.76 (d, 1 H, H-1?), 4.39ꢀ3.51 (m, 13 H),
4.52ꢀ
1.44, 1.43, 1.33, 1.15 (4 s, 12 H, 4 CH3); 13C NMR (100
MHz, CDCl3): d 170.8, 169.2, 168.4, (3 C, 3 CH3COÃ),
166.2, 165.0, 164.9, 164.6, (4 C, 4 COPh), 117.5(CH2Ä
CH2) 112.0, 108.3 (2 C, 2 C(CH3)), 104.9, 100.6,
/3.45 (m, 21 H), 1.89, 1.85, 1.79 (3 s, 9 H, CH3CO),
product 7 (6.02 g, 92.1%) as a syrup: [a]D
ꢁ
/
1
/
/
/
/
/
CHÃ
/
/
99.6, 98.2 (4 C, 4 C-1), 101.1 (1 C, PhCH), 82.1, 80.5,
/
/
79.6. 79.3, 78.0, 77.9, 73.9, 73.7, 73.1, 72.5, 72.0, 71.8,
71.1, 68.7, 68.5, 66.6, 66.4, 63.3, 62.3 (C-2ꢀ6), 26.9, 26.7,
26.0, 25.4, 20.7, 20.6. Anal. Calcd for C74H80O28: C,
62.71; H, 5.65. Found: C, 62.97; H, 5.75.
1.42 (2 s, 6 H, CH3), 1.35 (s, 3 H, CH3), 1.11 (s, 3 H,
CH3). Anal. Calcd for C35H42O12: C, 64.22; H, 6.42.
Found: C, 64.37; H, 6.57.
/
3.7. 2-O-Benzoyl-4,6-O-benzylidene-b-
glucopyranosyl-(103)-1,2:5,6-di-O-isopropylidene-a-
glucofuranose (8)
D
-
3.9. 3-O-Allyl-2,4,6-tri-O-benzoyl-b-
(103)-2,4,6-tri-O-acetyl-b- -glucopyranosyl-(10
O-benzoyl-4,6-di-O-acetyl-b- -glucopyranosyl-(10
1,2,4,6-tetra-O-acetyl- -glucopyranose (10)
D
-glucopyranosyl-
3)-2-
3)-
/
D-
/
D
/
D
/
D
To a soln of compound 7 (5.45 g, 8.33 mmol) in MeOH
(20 mL) was added PdCl2 (450 mg, 2.55 mmol). After
stirring the mixture for 4 h at rt, TLC (1:1 petroleum
A mixture of 9 (3.55 g, 2.5 mmol) and 80% HOAcꢀ
/
H2O
(80 mL) was refluxed for 3ꢀ4 h, then concentrated to
/
etherꢀ
/
EtOAc) indicated that the reaction was complete.
dryness. The residue was dissolved in pyridine (50 mL),
and Ac2O (15 mL, 0.16 mol) was added. After stirring
The mixture was filtered and the soln was concentrated
to dryness. The resultant residue was purified by flash
the mixture at rt for 12 h, TLC (2:1 petroleum etherꢀ
/
chromatography (1:1 petroleum etherꢀ
(3.68 g, 78.5%): [a]D 298 (c 0.5, CHCl3); H NMR
(400 MHz, CDCl3): d 8.09ꢀ7.38 (m, 10 H, 2 PhH), 5.59
(s, 1 H, PhCH), 5.44 (d, 1 H, J1,2 3.6, H-1), 5.16 (dd, 1
H, J2,3 J1,2 7.8 Hz, H-2?), 4.81 (d, 1 H, J1,2 7.8 Hz,
H-1?), 4.40ꢀ3.55 (m, 12 H), 1.43 (s, 3 H, CH3), 1.42 (s, 3
/
EtOAc) to give 8
EtOAc) indicated that the reaction was complete. The
reaction mixture was concentrated to dryness, and the
residue was purified by flash column chromatography
1
ꢁ
/
/
on a silica gel column (1:1 petroleum etherꢀEtOAc) to
/
ꢄ
/
ꢄ
/
give compound 10 (3.22 g, 89.8% for two steps) as an
anomeric mixture that was used for further reaction.
/
H, CH3), 1.34 (s, 3 H, CH3), 1.14 (s, 3 H, CH3). Anal.
Calcd for C32H38O12: C, 67.84; H, 6.71. Found: C,
67.66; H, 6.78.
Pure a-anomer was isolated as a foamy solid: [a]D
ꢁ
/
488
(c 1.0, CHCl3); H NMR (400 MHz, CDCl3): d 7.98ꢀ
7.40 (m, 20 H, 4 PhH), 6.16 (d, 1 H, J1,2 3.6 Hz, H-1),
1
/

W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ
/2823
2819
5.58ꢀ
J3,4
9.6 Hz, H-2§), 5.07ꢀ
/
5.46 (m, 1H, CH2Ä
J4,5
9.6 Hz, H-4§), 5.12 (dd, 1 H, J1,2 8.0, J2,3
4.70 (m, 8 H, CH2ÄCHÃCH2, H-2,
/
CH Ã
/
CH2), 5.41 (dd, 1 H,
3.11. 3-O-Allyl-2,4,6-tri-O-benzoyl-b-
(103)-2,4,6-tri-O-acetyl-b-
O-benzoyl-4,6-di-O-acetyl-b-
2,4,6-tri-O-acetyl-a- -glucopyranosyl
trichloroacetimidate (12)
D
-glucopyranosyl-
/
D
-glucopyranosyl-(10
-glucopyranosyl-(10
/3)-2-
ꢄ
/
ꢄ
/
D
/3)-
/
/
/
D
H-2?, H-2ƒ, H-4, H-4?, H-4ƒ), 4.64 (d,1 H, J1,2 8.0 Hz, H-
1§), 4.49 (d, 1 H, J1,2 7.8 Hz, H-1?), 4.37 (d, 1 H, J1,2 8.1
Hz, H-1ƒ), 4.50ꢀ
/
4.38 (m, 18 H,), 2.12, 2.06, 2.06, 2.04,
2.03, 2.01, 1.94, 1.82, 1.81 (9 s, 27 H, 9 CH3CO); 13C
NMR (100 MHz, CDCl3): d 170.8, 170.7, 170.7, 169.2,
Compound 11 (1.66 g, 1.20 mmol) was dissolved in
CH2Cl2 (30 mL), then CCl3CN (0.4 mL, 6.2 mmol) and
DBU ( 60 mL, 0.5 mmol) were added. The reaction
mixture was stirred for 2 h, at the end of which time
169.1, 169.0, 168.8, 168.7, 168.4, (9 C, 9 CH3COÃ
166.2, 166.0, 165.0, 164.6 (4 C, 4 COPh), 117.5 (CH2Ä
CHÃCH2), 101.0, 100.8, 100.6, 89.2 (4 C, 4 C-1), 79.6,
/),
/
TLC (1:1 petroleum etherꢀEtOAc) indicated that the
/
/
reaction was complete. The mixture was concentrated
and the residue was purified by flash chromatography
78.3, 77.7, 77.5, 75.3, 74.5, 73.6, 73.2, 72.2, 72.1, 72.0,
71.7, 71.6, 71.0, 70.0, 68.7, 68.4, 67.5, 63.3, 62.2, 62.2,
61.9, 60.4, 21.1, 20.9, 20.8, 20.6. Anal. Calcd for
C73H80O34: C, 58.40; H, 5.33. Found: C, 58.66; H, 5.45.
(1:1 petroleum etherꢀ
as a syrup: [a]D 408 (c 1.0, CHCl3); H NMR (400
MHz, CDCl3): d 8.64 (s, 1 H, CNHCCl3), 7.80ꢀ7.38 (m,
20 H, 4 PhH), 6.40 (d, 1 H, J1,2 3.6 Hz, H-1), 5.55ꢀ5.46
(m, 1 H, CH2ÄCH ÃCH2), 5.43 (dd, 1 H, J4,5 J3,4 9.6
Hz, H-4§), 5.09 (dd, 1 H, J2,3 9.4 Hz, H-2§), 5.09 (dd, 1
H, J4,5 J3,4
9.6 Hz, H-4ƒ), 5.03 (dd, 1 H, J1,2 7.8, J2,3
9.1 Hz, H-2?), 4.98ꢀ4.88 (m, 2 H, CH2ÄCHÃCH2),
4.92ꢀ4.73 (m, 2 H, H-2, H-4), 4.80 (dd, 1 H, J1,2 3.6 Hz,
/EtOAc) to give 12 (1.74 g, 80.1%)
1
ꢁ
/
/
/
/
/
ꢄ
/
ꢄ
/
3.10. 3-O-Allyl-2,4,6-tri-O-benzoyl-b-
(103)-2,4,6-tri-O-acetyl-b- -glucopyranosyl-(10
O-benzoyl-4,6-di-O-acetyl-b- -glucopyranosyl-(10
2,4,6-tri-O-acetyl- -glucopyranose (11)
D
-glucopyranosyl-
3)-2-
3)-
ꢄ
/
ꢄ
/
/
D
/
/
/
/
D
/
/
D
J2,3 9.6 Hz, H-2), 4.67 (d, 1 H, H-1§), 4.48 (d, 1 H, H-1?),
4.40 (d, 1 H, H-1ƒ), 4.52-3.50 (m, 18 H), 2.07, 2.06, 2.05,
2.02, 1.96, 1.83, 1.82, 1.80 (8 s, 24 H, 8 CH3CO); 13C
NMR (100 MHz, CDCl3): d 170.6, 170.5, 170.4, 169.1,
Compound 10 (3.08 g, 2.14 mmol) was dissolved in
60:20 satd NH3ꢀtolueneꢀMeOH (80 mL). The reaction
mixture was stirred for 40 min, at the end of which time
TLC (1:1 petroleum etherꢀEtOAc) indicated that the
reaction was complete. The mixture was concentrated to
dryness. Purification by silica gel column chromatogra-
/
/
169.0, 169.0, 168.9, 168.3 (8 C, 8 CH3COÃ
164.8, 164.8, 164.2 (4 C, 4 COPh), 133.9 (CH2Ä
CH2), 117.4 (CH2ÄCHÃCH2), 101.0, 100.6, 100.6, 92.8
(4 C, 4 C-1), 90.7 (ÃCCl3), 79.4, 78.3, 77.5., 77.2, 74.3,
/
), 166.0,
/
/
CHÃ
/
/
/
/
phy (1:2 petroleum etherꢀEtOAc) gave 11 as an
/
73.4, 73.1, 72.0, 71.9, 71.8, 71.7, 71.6, 71.0, 70.0, 68.5,
68.1, 67.0, 63.1, 62.1, 61.7, 20.6, 20.4, 20.4, 20.3, 20.2.
Anal. Calcd for C73H78Cl3NO33: C, 54.65; H, 4.87.
Found: C, 54.82; H, 4.90.
anomeric mixture (1.80 g, 60.2%) that was used for
further reaction. Pure a-anomer was isolated as a foamy
solid: [a]D ꢁ
PhH), 5.50 (m, 1 H, CH2Ä
J3,4 J4,5
9.6 Hz, H-4§), 5.30 (d, 1 H, J1,2
H-1), 5.10 (dd, 1 H, J1,2 8.2, J2,3 8.8 Hz, H-2§), 5.03ꢀ
4.55 (m, 8 H, CH2ÄCHÃCH2, H-2, H-2?, H-2ƒ, H-4, H-
4?, H-4ƒ), 4.65 (d,1 H, J1,2 8.0 Hz, H-1§), 4.44 (d, 1 H,
J1,2 7.8 Hz, H-1?), 4.40 (d, 1 H, J1,2 8.2 Hz, H-1ƒ), 4.48ꢀ
3.52 (m, 19 H, CH2ÄCHÃCH2, 4 H-3, 4 H-5, 8 H-6, Ã
/
548 (c 1.0, CHCl3); d 7.80ꢀ
CH ÃCH2), 5.42 (dd, 1 H,
3.2 Hz,
/
7.40 (m, 20 H, 4
/
/
ꢄ
/
ꢄ
/
ꢄ
/
3.12. Allyl 3-O-allyl-2,4,6-tri-O-benzoyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
a- -glucopyranoside (14)
D
-
-
/
/
D
/
/
/
3)-2-O-benzoyl-4,6-di-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-b-
3)-2-O-benzoyl-4,6-O-benzylidene-
D-
/
D-
/
/
/
/
/
D
OH), 2.06, 2.05, 2.04, 2.03, 2.01, 1.95, 1.88, 1.84 (8 s, 24
H, 8 CH3CO); 13C NMR (100 MHz, CDCl3): d 170.9,
170.6, 170.6, 169.3, 169.2, 169.1, 169.0, 168.3 (8 C, 8
Compound 12 (870 mg, 0.57 mmol) and 13 (270 mg,
0.65 mmol) were dried together under high vacuum for 2
h, then dissolved in anhyd CH2Cl2 (30.0 mL). Me3SiOTf
CH3COÃ
/
), 166.1, 164.9, 164.8, 164.3 (4 C, 4 COPh),
(10.0 mL, 0.087 mmol) was added dropwise at ꢃ20 8C
/
133.9 (CH2Ä
/
CHÃCH2), 117.5 (CH2ÄCHÃCH2), 101.0,
/
/
/
with N2 protection. The reaction mixture was stirred for
3 h, during which time the temperature was gradually
raised to ambient temperature. Then the mixture was
neutralized with Et3N. Concentration of the reaction
mixture, followed by purification on a silica gel column
100.7, 100.6, 89.6 (4 C, 4 C-1), 79.5, 78.6, 77.6, 75.1,
74.4, 73.3, 73.1, 72.0, 71.9, 71.8, 71.7, 71.4, 71.0, 68.3,
68.1, 67.9, 67.1, 63.1, 62.2, 62.0, 60.4 (C-2ꢀ6), 20.8, 20.7,
/
20.6, 20.5, 20.4, 20.4, 20.3. Anal. Calcd for C71H78O33:
C, 58.44; H, 5.35. Found: C, 58.33; H, 5.44.
with 2:1 petroleum etherꢀ
/
EtOAc as the eluent gave the
628 (c 1.0,
CHCl3); H NMR (400 MHz, CDCl3): d 8.60ꢀ7.32 (m,
30 H, 6 PhH), 5.82ꢀ5.74 (m, 1 H, CH2ÄCH ÃCH2),
5.54ꢀ5.44 (m, 1 H, CH2ÄCH ÃCH2), 5.50 (s, 1 H,
product 14 (850 mg, 85.5%) as a syrup: [a]D ꢁ
/
1
/
/
/
/
/
/
/

2820
W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ2823
/
PhCH), 5.42 (dd, 1 H, J4,5
ꢄ
/
J3,4
ꢄ
/
9.4 Hz, H-4V), 5.25ꢀ
CH2), 5.10 (d, 1 H, J1,2 3.6 Hz,
/
3.14. Allyl 3-O-allyl-2,4,6-tri-O-benzoyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (17)
D
-
-
/
D
5.09 (m, 2 H, CH2Ä
/
CHÃ
/
H-1), 5.07 (dd, 1 H, J2,3 9.6, J1,2 7.8 Hz, H-2V), 4.98ꢀ
/
/
3)-2-O-benzoyl-4,6-di-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
3)-2,4,6-tri-O-acetyl-b-
6)]-2-O-benzoyl-a-
D-
CH2, H-2IꢀIV, H-4IIꢀIV), 4.59
/
D-
4.70 (m, 9 H, CH2Ä
/
CHÃ
/
(d, 1 H, J1,2 7.8Hz, H-1V), 4.42 (d, 1 H, J1,2 8.0 Hz, H-
1II), 4.34 (d, 1 H, J1,2 7.3 Hz, H-1III), 4.30 (d, 1 H, J1,2
/
D-
/
D-
6.0 Hz, H-1I), 4.50ꢀ
3.46 (m, 25 H), 2.04, 2.04, 2.03, 1.94,
/
/
D-
1.94, 1.91, 1.81, 1.80 (8 s, 24 H, 8 CH3CO); 13C NMR
(100 MHz, CDCl3): d 170.9, 170.8, 170.7, 169.2, 169.1,
Compounds 15 (470 mg, 0.28 mmol) and 16 (340 mg,
0.33 mmol) were dried together under high vacuum for 2
h, then dissolved in anhyd CH2Cl2 (30.0 mL). Me3SiOTf
168.4, 168.2, 168.1 (8 C, 8 CH3COÃ
165.0, 164.7 (4 C, 4 COPh), 137.3, 134.0 (2 C, CH2Ä
CHÃCH2), 118.2, 117.5 (2 C, CH2ÄCHÃCH2), 101.2 (Ã
CHPh), 101.0, 100.7, 100.6, 99.9 (4 C, b C-1), 95.8 (1 C,
a C-1), 79.6, 79.1, 78.3, 77.4, 74.8, 74.1, 74.0, 73.5, 73.2,
72.5, 72.0, 71.7, 71.0, 68.9, 68.5, 68.3, 63.2, 62.8, 62.6,
/
), 166.2, 165.7,
/
/
/
/
/
(10.0 mL, 0.087 mmol) was added dropwise at ꢃ20 8C
/
with N2 protection. The reaction mixture was stirred for
3 h, during which time the temperature was gradually
raised to ambient temperature. Then the mixture was
neutralized with Et3N. Concentration of the reaction
mixture, followed by purification of the product on a
62.1, 62.0, 61.9 (C-2ꢀ/6), 20.8, 20.6. Anal. Calcd for
C94H100O39: C, 60.91; H, 5.40. Found: C, 61.18; H, 5.44.
silica gel column with 2:1 petroleum etherꢀ
/
EtOAc as the
758 (c
1.0, CHCl3); H NMR (400 MHz, CDCl3): d 8.03ꢀ7.38
(m, 45 H, 9 PhH), 5.91 (dd, 1 H, J4,5 J3,4 9.6 Hz, H-
4), 5.73ꢀ5.62 (m, 1 H, CH2CH ÄCH2), 5.54ꢀ5.45 (m, 1
H, CH2CH ÄCH2), 5.66 (dd, 1 H, J2,3 J3,4 9.4 Hz,
H-3), 5.53 (dd, 1 H, J1,2 J2,3 9.4 Hz), 5.20ꢀ4.76 (m,
17 H), 4.97 (d, 1 H, J1,2 3.4 Hz, H-1), 4.57ꢀ3.21 (m, 30
eluent gave 17 (220 mg, 65.5%) as a syrup: [a]D
ꢁ
/
1
/
3.13. Allyl 3-O-allyl-2,4,6-tri-O-benzoyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
(15)
D
-
-
ꢄ
/
ꢄ
/
/
D
/
/
/
/
3)-2-O-benzoyl-4,6-di-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-b-
3)-2-O-benzoyl-a- -glucopyranoside
D-
/
ꢄ
/
ꢄ
/
/
D-
ꢄ
/
ꢄ
/
/
/
D
/
H), 4.56 (d, 1 H, J1,2 8.2 Hz, H-1), 4.46 (d, 1 H, J1,2 7.8
Hz, H-1), 4.41 (d, 1 H, J1,2 8.0 Hz, H-1), 4.36 (d, 1 H,
J1,2 7.3 Hz, H-1), 4.34 (d, 1 H, J1,2 7.9 Hz, H-1), 4.29 (d,
1 H, J1,2 8.0 Hz, H-1), 2.05, 2.05, 2.04, 2.03, 2.00, 1.94,
1.90, 1.88, 1.85, 1.83, 1.79 (11 s, 33 H, 11 CH3CO); 13C
NMR (100 MHz, CDCl3): d 171.2, 171.1, 170.8, 170.8,
170.7, 169.2, 169.1, 169.0, 168.4, 168.2, 168.1 (11 C, 11
CH3CO), 166.2, 166.1, 165.5, 165.3, 165.1, 165.0, 164.9,
To a soln of 90% HOAc (30 mL) was added 14 (800 mg,
0.45 mmol), and the mixture was stirred at 40 8C
overnight, then concentrated to dryness. The residue
was passed through a short silica column (1:2 petroleum
etherꢀ
solid: [a]D
CDCl3): d 8.04ꢀ
H, CH2ÃCH ÄCH2), 5.54ꢀ
CH2), 5.42 (dd, 1 H, J4,5
4.84 (m, 4 H, CH2CHÄCH2), 5.08 (d, 1 H, J1,2 3.6 Hz,
H-1), 5.08ꢀ4.70 (m, 8 H), 4.66 (d, 1 H, J1,2 8.2 Hz, H-
1V), 4.52 (d, 1 H, J1,2 7.8 Hz, H-1III), 4.48 (d, 1 H, J1,2
8.0 Hz, H-1IV), 4.42 (d, 1 H, J1,2 7.3 Hz, H-1II), 4.50ꢀ
/
EtOAc) to give 15 (720 mg, 93%) as a foamy
1
ꢁ
/
678 (c 1.0, CHCl3); H NMR (400 MHz,
7.39 (m, 25 H, 5 PhH), 5.81ꢀ5.74 (m, 1
5.43 (m, 1 H, CH2ÃCH Ä
J3,4
9.4 Hz, H-4V), 5.25ꢀ
/
/
164.9, 164.3 (9 C, 9 COPh), 134.7, 133.6 (2 C, CH2Ä
/
/
/
/
/
/
CHÃCH2), 118.0, 117.5 (2 C, CH2ÄCHÃCH2), 101.6,
/
/
/
ꢄ
/
ꢄ
/
/
101.3, 101.1, 101.1, 100.7, 100.2 (6 C, b C-1), 94.4 (1 C, a
C-1), 82.3, 79.6, 78.3, 77.8, 73.9, 73.5, 73.2, 73.1, 72.8,
72.4, 72.0, 72.0, 71.8, 71.1, 71.0, 69.6, 68.6, 68.5, 63.4,
/
/
63.3, 63.2, 63.2, 62.8, 62.4, 62.1, 62.0, 60.5 (C-2ꢀ
20.7, 20.7, 20.6, 20.6, 20.5, 20.0. Anal. Calcd for
133H138O56: C, 60.68; H, 5.25. Found: C, 60.44; H,
/6), 20.8,
/
3.36 (m, 27 H), 2.08, 2.06, 2.05, 2.04, 2.01, 1.92, 1.82,
1.79 (8 s, 24 H, CH3CO); 13C NMR (100 MHz, CDCl3):
d 170.7, 170.7, 169.2, 169.1, 169.0, 168.4, 168.2, 168.1 (8
C, 8 CH3CO), 166.2, 165.5, 165.0, 165.0, 164.4 (5 C, 5
C
5.35.
3.15. b-
D
-Glucopyranosyl-(10
/
3)-b-
D
-glucopyranosyl-
-glucopyranosyl-
-glucopyranosyl-
(10
(10
(10
/
3)-b-
3)-[b-
6)]-b-
D
-glucopyranosyl-(10
/3)-b-D
COPh), 134.7, 133.6 (2 C, CH2Ä
(2 C, CH2ÄCHÃCH2), 101.1, 101.0, 100.7, 99.8 (4 C, b
/
CHÃ
/
CH2), 118.0, 117.5
/
D-glucopyranosyl-(10
/
3)-b-D
/
/
/
D-glucopyranose (18)
C-1), 95.0 (1 C, a C-1), 82.3, 79.6, 78.3, 77.8, 73.9, 73.5,
73.2, 73.1, 72.8, 72.4, 72.0, 72.0, 71.8, 71.1, 71.0, 69.6,
68.6, 68.5, 63.4, 63.3, 63.2, 63.2, 62.8, 62.4, 62.1, 62.0,
To a soln of 17 (192 mg, 0.15 mmol) in MeOH (20 mL)
was added PdCl2 (100 mg, 0.64 mmol). After stirring the
60.5 (C-2ꢀ/6), 20.8, 20.6, 20.5, 20.0. Anal. Calcd for
mixture for 6 h at rt, TLC (1:2 petroleum etherꢀEtOAc)
/
C87H96O39: C, 59.18; H, 5.44. Found: C, 59.36; H, 5.57.
indicated that the reaction was complete. The mixture
was filtered, the soln was concentrated to dryness, and
the resultant residue was dissolved in a satd soln of NH3
in MeOH (15 mL). After a week at rt, the reaction

W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ
/2823
2821
mixture was concentrated, and the residue was purified
by chromatography on Sephadex LH-20 (MeOH) to
afford 18 (52 mg, 66.3% for two steps) as a foamy solid:
washed with satd aq NaHCO3 and water, then dried and
concentrated. Purification by column chromatography
with 2:1 petroleum etherꢀEtOAc as the eluent afforded
/
1
[a]D
ꢃ
/
1.38 (c 1.0, H2O); H NMR (400 MHz, D2O): d
compound 20 (1.6 g, 79%) as a syrup: [a]D20
ꢁ
/
30.68 (c,
H,
9.6 Hz, H-3?), 5.63
9.6 Hz, H-4?), 5.62 (d, 1 H, J1,2 3.6
1
4.73 (d, 1 H, J 7.8 Hz, H-1), 4.72ꢀ
/
4.69 (m, 5 H, H-1),
1.5, CHCl3); H NMR d: 7.96ꢀ
/
7.05 (m, 30 H, 5 BzÃ
/
4.66 (d, 1 H, J 8.0 Hz, H-1), 3.87ꢀ
/
3.30 (m, 42 H); 13C
NMR: d 102.4, 102.4, 102.3, 102.3, 102.2, 102.2, 102.1
(7 C-1), 84.2, 84.1, 83.9, 83.7, 75.6, 75.2, 75.2, 73.1, 72.9,
PhÃ
/
H), 5.78 (dd, 1 H, J2,3
ꢄ/J3,4
ꢄ
/
(dd, 1 H, J3,4
ꢄ/J4,5
ꢄ
/
Hz, H-1), 5.62 (s, 1 H, PhCH), 5.52 (dd, 1 H, J1,2 8.0,
J2,3 9.6 Hz, H-2?), 5.15 (d, 1 H, J1,2 8.0 Hz, H-1?), 5.03
72.8, 72.4, 69.2, 67.7, 60.4, 60.3, 60.2, (C-2ꢀ6). Anal.
/
Calcd for C42H72O36: C, 43.75; H, 6.25. Found: C,
43.56, H, 6.14.
(dd, 1 H, J1,2 3.6, J2,3 9.8 Hz, H-2), 4.55ꢀ3.77 (m, 8 H,
H-3, 4, 5, 5?, 6, 6?). Anal. Calcd for C54H46O16: C, 68.20;
H, 4.88. Found: C, 68.36; H, 4.94.
/
3.16. Allyl 2,3,4,6-tetra-O-benzoyl-b-
(103)-2-O-benzoyl-4,6-O-benzylidene-a-
glucopyranoside (19)
D-glucopyranosyl-
/
D-
3.18. 2,3,4,6-Tetra-O-benzoyl-b-
3)-2-O-benzoyl-4,6-O-benzylidene-a-D-glucopyranosyl
D
-glucopyranosyl-(10
/
trichloroacetimidate (21)
To a soln of compounds 13 (1.0 g, 2.43 mmol) and
-glucopyranosyl trichloro-
acetimidate (2.1 g, 2.80 mmol) in CH2Cl2 (30 mL) was
2,3,4,6-tetra-O-benzoyl-a-
D
To a soln of compound 20 (1.5 g, 1.58 mmol) in dry
CH2Cl2 (25 mL) were added CCl3CN (0.5 mL, 5.0
mmol) and DBU (40 mL). The mixture was stirred at rt
for 2 h, at the end of which time TLC (3:1 petroleum
added 4A molecular sieves (1.0 g). The mixture was
stirred and cooled to ꢃ10 8C under N2 protection, and
/
Me3SiOTf (50 mL, 0.28 mmol) was added. Stirring was
continued at the low temperature for 1 h, at the end of
etherꢀEtOAc) indicated that the reaction was complete.
The mixture was concentrated, and the residue thus
obtained was subjected to column chromatography with
/
which time TLC (3:1 petroleum etherꢀEtOAc) indicated
/
that the reaction was complete. Et3N was added to
quench the reaction, the mixture was filtered, and the
filter cake was washed with CH2Cl2. The combined
filtrate and washings were washed with satd aq
NaHCO3 and water, then dried and concentrated.
Purification by column chromatography with 3:1 petro-
3:1 petroleum etherꢀ
was obtained as a syrup (1.40 g, 81%): [a]D20
1.0, CHCl3); 1H NMR d: 8.49 (s, 1 H, CNHCCl3),
7.96ꢀ7.08 (m, 30 H, 5 BzÃH, PhÃH), 6.52 (d, 1 H, J1,2
3.6 Hz, H-1), 5.78 (dd, 1 H, J2,3 J3,4 9.6 Hz, H-3?), 5.67
(s, 1 H, PhCH), 5.62 (dd, 1 H, J3,4 J4,5 9.6 Hz, H-
/
EtOAc as the eluent. Compound 21
ꢁ
/
39.98 (c,
/
/
/
ꢄ
/
ꢄ
/
ꢄ
/
leum etherꢀ
(2.2 g, 91%) as a syrup: [a]D20
NMR d: 7.96ꢀ7.06 (m, 30 H, 5 BzÃ
1 H, J2,3 J3,4 9.6 Hz, H-3?), 5.77ꢀ
CH2ÄCH ÃCH2), 5.64 (dd, 1 H, J3,4 J4,5
4?), 5.64 (s, 1 H, PhCH), 5.52 (dd, 1 H, J1,2 8.0, J2,3 9.6
Hz, H-2?), 5.21ꢀ CH2), 5.15 (d,
/
EtOAc as the eluent afforded compound 19
22.28 (c, 1.5, CHCl3); 1H
H, PhÃH), 5.78 (dd,
5.67 (m, 1 H,
9.6 Hz, H-
4?), 5.52 (dd, 1 H, J1,2 8.0 Hz, J2,3 9.6 Hz, H-2?), 5.32
(dd, 1 H, J1,2 3.6, J2,3 9.6 Hz, H-2), 5.14 (d, 1 H, J1,2 8.0
Hz, H-1?), 4.57 (dd, 1 H, J5,6a 3.6, J6a,6b 12.0 Hz, H-6?a),
ꢁ
/
/
/
/
ꢄ
/
ꢄ
/
/
4.50 (dd, 1 H, J2,3
H, H-6a, 6?b), 4.11ꢀ
J3,4 J4,5 9.6 Hz, H-4), 3.84 (dd, 1 H, J5,6b 10.3, J6a,6b
ꢄ
/
J3,4 9.6 Hz, H-3), 4.38ꢀ/4.34 (m, 2
/
/
ꢄ
/
ꢄ
/
/
4.05 (m, 2 H, H-5, 5?), 3.96 (dd, 1 H,
ꢄ
/
ꢄ
/
/
5.05 (m, 2 H, CH2Ä
/
CHÃ
/
10.3 Hz, H-6b). Anal. Calcd for C56H46Cl3NO16: C,
61.13; H, 5.25. Found: C, 61.26; H, 5.33.
1 H, J1,2 8.0 Hz, H-1?), 5.13 (d, 1 H, J1,2 3.6 Hz, H-1),
5.05 (dd, 1 H, J1,2 3.6, J2,3 9.8 Hz, H-2), 4.54 (dd, 1 H,
J5,6a 3.6, J6a,6b 12.0 Hz, H-6?a), 4.50 (dd, 1 H, J2,3
J3,4 9.8 Hz, H-3), 4.39 (dd, 1 H, J5,6b 4.9, J6a,6b 12.0
Hz, H-6?b), 4.28 (dd, 1 H, J5,6a 4.6, J6a,6b 10.2 Hz, H-6a),
CH2, H-4, 5, 5?, 6b). Anal.
Calcd for C57H50O16: C, 69.08; H, 5.09. Found: C,
69.16; H, 5.23.
ꢄ
/
3.19. Allyl 4,6-di-O-acetyl-2-O-benzoyl-3-O-
ꢄ
/
chloroacetyl-b-
2-O-benzoyl-b-
4,6-O-benzylidene-a-
D
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranoside (24)
/
3)-4,6-di-O-acetyl-
3)-2-O-benzoyl-
D
/
4.15-3.78 (m, 6 H, CH2Ä
/
CHÃ
/
D
To a soln of compounds 23 (240 mg, 0.58 mmol) and 22
(500 mg, 0.53 mmol) in CH2Cl2 (20 mL) was added 4A
molecular sieves (0.5 g). The mixture was stirred and
3.17. 2,3,4,6-Tetra-O-benzoyl-b-
3)-2-O-benzoyl-4,6-O-benzylidene-
D
-glucopyranosyl-(10
/
D
-glucopyranose (20)
cooled to ꢃ10 8C under N2 protection, and Me3SiOTf
/
(10 mL, 0.056 mmol) was added. Stirring was continued
at the low temperature for 2 h, at the end of which time
To a soln of sodium acetate (670 mg, 8.17 mmol) and
PdCl2 (750 mg, 4.23 mmol) in AcOH (90%, 10 mL) was
added compound 19 (2.1 g, 2.12 mmol). The mixture
was stirred at rt overnight under N2 protection. TLC
TLC (2:1 petroleum etherꢀEtOAc) indicated that the
/
reaction was complete. Et3N was added to quench the
reaction, the mixture was filtered, and the filter cake was
washed with CH2Cl2. The combined filtrate and wash-
ings were washed with satd aq NaHCO3 and water, then
dried and concentrated. Purification of the product by
(2:1 petroleum etherꢀEtOAc) indicated that the reaction
/
was complete. The mixture was filtered, and the filter
cake was washed with CH2Cl2. The organic phase was

2822
W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ2823
/
column chromatography with 2:1 petroleum etherꢀ
/
CH2Cl2. The combined filtrate and washings were
washed with satd aq NaHCO3 and water, then dried
and concentrated. Purification by column chromatogra-
EtOAc as the eluent afforded compound 24 (500 mg,
1
79%) as a syrup: [a]D20/
d: 7.80ꢀ7.17 (m, 40 H, 7 BzÃ
H, CH2ÄCH ÃCH2), 5.52 (s, 1 H, PhCH), 5.17ꢀ
8 H, CH2ÄCHÃCH2, H-1, 2?, 2ƒ, 3ƒ, 4?, 4ƒ), 4.81, 4.61 (2
d, 2 H, J1,2 8.0 Hz, H-1?, 1ƒ), 4.79 (dd, 1 H, J1,2 3.9, J2,3
9.6 Hz, H-2), 4.40ꢀ3.59 (m, 14 H, CH2ÄCHÃCH2, H-3,
ꢁ
/
36.08 (c, 0.5, CHCl3); H NMR
H, PhÃH), 5.73ꢀ5.63 (m, 1
5.02 (m,
/
/
/
/
phy with 2:1 petroleum etherꢀEtOAc as the eluent
/
/
/
/
afforded compound 26 (400 mg, 73.6%) as a syrup: [a]D20/
1
/
/
ꢁ
/
16.68 (c, 1.2, CHCl3); H NMR d: 7.90ꢀ
/
7.09 (m, 50
5.63 (m, 1 H, CH2ÄCH Ã
5.50 (m, 2 H, H-3V, 4V), 5.52, 5.48 (2 s, 2 H,
2 PhCH), 5.32 (dd, 1 H, J2,3 9.6, J1,2 8.0 Hz, H-2V),
5.15ꢀ4.80 (m, 7 H, CH2ÄCHÃCH2Ã
, H-2IIꢀIV, 4II,III),
5.02 (d, 1 H, J1,2 3.6 Hz, H-1), 4.75, 4.74, 4.45, 4.45 (4 d,
4 H, Jꢄ
8.0 Hz, H-1IIꢀV), 4.69 (dd, 1 H, J1,2 3.6, J2,,3 9.6
Hz, H-2I), 4.39ꢀ
CH2, H-
H, 8 BzÃ
CH2), 5.54ꢀ
/
H, 2 PhÃ
/
H), 5.73ꢀ
/
/
/
/
/
/
/
3?, 4, 5, 5?, 5ƒ, 6, 6?, 6ƒ), 3.78, 3.71 (ABq, 2 H, J 14.8 Hz,
ClCH2CO), 2.04, 1.99, 1.98, 1.97 (4 s, 12 H, 4 CH3CO).
Anal. Calcd for C59H61ClO24: C, 59.57; H, 5.17. Found:
C, 59.44; H, 5.07.
/
/
/
/
/
/
3.24 (m, 23 H, CH2Ä
/
CHÃ
/
3.20. Allyl 4,6-di-O-acetyl-2-O-benzoyl-b-
glucopyranosyl-(103)-4,6-di-O-acetyl-2-O-benzoyl-b-
glucopyranosyl-(103)-2-O-benzoyl-4,6-O-benzylidene-
a- -glucopyranoside (25)
D-
3IꢀIV, 4I,IV, 5IꢀV, 6IꢀV), 2.02, 1.94, 1.92, 1.89 (4 s, 12 H,
4 CH3CO). Anal. Calcd for C111H104O38: C, 65.16; H,
5.12. Found: C, 65.06; H, 4.98.
/
D-
/
D
3.22. Allyl 2,3,4,6-tetra-O-benzoyl-b-D-glucopyranosyl-
Compound 24 (450 mg, 0.38 mmol) was dissolved in
mixed solvents of CH2Cl2 (4 mL) and MeOH (6 mL). To
the soln were added thiourea (145 mg, 1.91 mmol) and
2,4-lutidine (42 mL, 0.38 mmol), and the reaction
mixture was boiled under reflux for 16 h, at the end of
(10
/
3)-2-O-benzoyl-b-
D
-glucopyranosyl-(10
/
3)-4,6-di-
O-acetyl-2-O-benzoyl-b-
O-acetyl-2-O-benzoyl-b-
benzoyl-a-D-glucopyranoside (27)
D
-glucopyranosyl-(10
/3)-4,6-di-
D-glucopyranosyl-(10
/
3)-2-O-
which time TLC (1.5:1 petroleum etherꢀ
/
EtOAc) indi-
To a soln of compounds 26 (350 mg, 0.171 mmol) and
ethylene glycol (0.1 mL, 1.80 mmol) in CH3CN (5 mL)
cated that the reaction was complete. The mixture was
concentrated and extracted with CH2Cl2, the organic
phase was washed sequentially with N HCl, satd aq
NaHCO3, and water, then dried and concentrated.
Purification by column chromatography with 2:1 petro-
was added p-TsOH×
/
H2O (10 mg). The mixture was
stirred at rt overnight. TLC (1:2 petroleum etherꢀ
/
EtOAc) indicated that the reaction was complete. The
mixture was neutralized with Et3N, concentrated and
extracted with CH2Cl2. The organic phase was washed
with water, then dried and concentrated. Purification by
leum etherꢀ
84%) as a syrup: [a]D20
d: 7.82ꢀ7.20 (m, 40 H, 7 BzÃ
H, CH2ÄCH ÃCH2), 5.54 (s, 1 H, PhCH), 5.21ꢀ
7 H, CH2ÄCHÃCH2, H-2, 2?, 2ƒ, 4?, 4ƒ), 5.08 (d, 1 H,
J1,2 3.6 Hz, H-1), 4.84, 4.59 (2 d, 2 H, J1,2 8.0 Hz, H-1?,
1ƒ), 4.40ꢀ3.47 (m, 15 H, CH2ÄCHÃCH2, H-3, 3?, 3ƒ, 4,
/
EtOAc as the eluent afforded 25 (360 mg,
35.38 (c, 0.7, CHCl3); 1H NMR
H, PhÃH), 5.76ꢀ5.66 (m, 1
4.85 (m,
ꢁ
/
/
/
/
/
column chromatography with 1:3 petroleum etherꢀ
EtOAc as the eluent afforded compound 27 (240 mg,
75%) as a syrup: [a]D20 18.98 (c, 0.8, CHCl3); 1H NMR
d: 8.09ꢀ7.01 (m, 40 H, 8 BzÃH), 5.73ꢀ5.63 (m, 1 H,
CH2ÄCH ÃCH2Ã), 5.67 (dd, 1 H, J2,3 J3,4 9.8 Hz,
H-3V), 5.52 (dd, 1 H, J3,4 9.8 Hz, H-4V), 5.38
J4,5
(dd, 1 H, J1,2 8.0, J2,3 9.8 Hz, H-2V), 5.16ꢀ
5.01 (m, 2 H,
/
/
/
/
/
/
ꢁ
/
/
/
/
/
/
/
/
/
/
ꢄ
/
ꢄ
/
5, 5?, 5ƒ, 6, 6?, 6ƒ), 2.05, 2.04, 1.99, 1.98 (4 s, 12 H, 4
CH3CO). Anal. Calcd for C57H60O23: C, 61.50; H, 5.43.
Found: C, 61.76; H, 5.48.
ꢄ
/
ꢄ
/
/
CH2Ä
/
CHÃ
/
CH2), 5.00 (d, 1 H, J1,2 3.6 Hz, H-1), 4.97ꢀ
/
4.73 (m, 5 H, H-2IIꢀIV, 4II,III), 4.71 (dd, 1 H, J1,2 3.6, J2,3
9.6 Hz, H-2I), 4.62, 4.61, 4.49, 4.36 (4 d, 4 H, J1,2 8.0 Hz,
3.21. Allyl 2,3,4,6-tetra-O-benzoyl-b-
(103)-2-O-benzoyl-4,6-O-benzylidene-b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
a- -glucopyranoside (26)
D-glucopyranosyl-
/
D-
H-1IIꢀV), 4.35ꢀ
/
3.19 (m, 23 H, CH2Ä
/
CHÃ
/
CH2Ã/, H-
/
3)-4,6-di-O-acetyl-2-O-benzoyl-b-
3)-4,6-di-O-acetyl-2-O-benzoyl-b-
3)-2-O-benzoyl-4,6-O-benzylidene-
D
D
-
-
3IꢀIV, 4I,IV, 5IꢀV, 6IꢀV), 2.07, 2.06, 1.96, 1.81 (4 s, 12 H,
4 CH3CO). Anal. Calcd for C97H96O38: C, 62.31; H,
5.17. Found: C, 62.45; H, 5.24.
/
/
D
3.23. Allyl 2,3,4,6-tetra-O-benzoyl-b-
(103)-[2,3,4,6-tetra-O-benzoyl-b- -glucopyranosyl-(10
6)]-2-O-benzoyl-b- 3)-4,6-di-O-
-glucopyranosyl-(103)-4,6-di-O-
-glucopyranosyl-(103)-[2,3,4,6-
6)]-2-O-
D-glucopyranosyl-
To a soln of compounds 25 (300 mg, 0.27 mmol) and 21
(350 mg, 0.32 mmol) in CH2Cl2 (15 mL) was added 4A
molecular sieves (0.5 g). The mixture was stirred and
/
D
/
D
-glucopyranosyl-(10
/
acetyl-2-O-benzoyl-b-
acetyl-2-O-benzoyl-b-
tetra-O-benzoyl-b-
D
/
cooled to ꢃ
(7.5 mL, 0.041 mmol) was added. Stirring was continued
at ꢃ10 8C for 4 h, at the end of which time TLC (2:1
petroleum etherꢀEtOAc) indicated that the reaction was
/
10 8C under N2 protection, and Me3SiOTf
D
/
D
-glucopyranosyl-(10
/
/
benzoyl-a-D-glucopyranoside (28)
/
complete. Et3N was added to quench the reaction, the
mixture was filtered, and the filter cake was washed with
To a soln of compounds 27 (200 mg, 0.107 mmol) and
2,3,4,6-tetra-O-benzoyl-a- -glucopyranosyl trichloro-
D

W. Zhao et al. / Carbohydrate Research 338 (2003) 2813ꢀ
/2823
2823
acetimidate (200 mg, 0.266 mmol) in CH2Cl2 (15 mL)
was added 4A molecular sieves (0.3 g). The mixture was
4.29ꢀ
4IꢀVII, 5IꢀVII, 6IꢀVII). 13C NMR d: 133.2 (s, 1 C, CH2Ä
CH2), 102.6, 102.5,
102.5, 102.3, 102.3, 102.3 (6 s, 6 C, C-1IIꢀVII), 97.03 (s, 1
C, C-1I), 84.53, 83.94, 83.80, 81.89 (4 s, 4 C, C-3IꢀIV),
60.53, 60.48, 60.48, 60.44, 60.44 (5 s, 5 C, C-6II,III,VꢀVII).
Anal. Calcd for C45H76O36: C, 45.30; H, 6.42. Found: C,
45.16; H, 6.24.
/
3.30 (m, 44 H, CH2Ä
/
CHÃ
/
CH2, H-2IꢀVII, 3IꢀVII
,
/
stirred and cooled to ꢃ
Me3SiOTf (7.5 mL, 0.041 mmol) was added. Stirring was
continued at ꢃ10 8C for 4 h, at the end of which time
TLC (1:1 petroleum etherꢀEtOAc) indicated that the
/
10 8C under N2 protection, and
CHÃ
/
CH2), 118.1 (s, 1 C, CH2Ä
/
CHÃ
/
/
/
reaction was complete. Et3N was added to quench the
reaction, the mixture was filtered, and the filter cake was
washed with CH2Cl2. The combined filtrate and wash-
ings were washed with satd aq NaHCO3 and water, then
dried and concentrated. Purification by column chro-
Acknowledgements
matography with 1:1 petroleum etherꢀ/EtOAc as the
eluent afforded compound 28 (220 mg, 68%) as a syrup:
1
This work was supported by The Chinese Academy of
Sciences (KZCX3-J-08) and by The National Natural
Science Foundation of China (Projects 30070185 and
39970864).
[a]2D0
80 H, 16 BzÃ
9.6 Hz, H-3), 5.68, 5.61, 5.55 (dd, 3 H, J3,4
Hz, H-4), 5.54, 5.48, 5.34 (dd, J1,2 8.0, J2,3 9.6 Hz, H-2),
5.53-5.43 (m, 1 H, CH2ÄCH ÃCH2), 5.01ꢀ4.24 (m, 15 H,
CH2ÄCHÃ 3.11 (m,
CH2, H-1IꢀVII, 2IꢀIV, 4II,III), 4.23ꢀ
29 H, CH2Ä
CH2, H-3IꢀIV, 4I,IV, 5IꢀVII, 6IꢀVII),
ꢁ
/
4.88 (c, 0.5, CHCl3); H NMR d: 8.10ꢀ
H), 5.94, 5.92, 5.77 (dd, 3 H, J2,3
J4,5
/
7.00 (m,
J3,4
9.6
/
ꢄ
/
ꢄ
/
ꢄ
/
ꢄ
/
/
/
/
/
/
/
/
CHÃ
/
References
2.03, 2.01, 1.94, 1.78 (4 s, 12 H, 4 CH3CO). 13C NMR d:
170.58, 170.58, 169.26, 169.15 (4 s, 4 C, 4 CH3CO),
166.12, 166.06, 165.92, 165.74, 165.74, 165.53, 165.23,
165.15, 165.11, 165.06, 164.90, 164.84, 164.72, 163.72,
163.57, 163.41 (16 s, 16 C, 16 BzCO), 117.30 (s, 1 C,
1. Chihara, G.; Maeda, Y.; Hamuro, J.; Sasaki, T.; Fukuoka,
F. Nature 1969, 222, 687ꢀ688.
/
2. Oka, M.; Hazama, S.; Suzuki, M.; Wang, F.; Wadamori,
K.; Lizuka, N.; Takeda, S.; Akitomi, Y.; Ohba, Y.;
Kajiwara, K.; Suga, T.; Suzuki, T. Int. J. Immunopharma-
CH2Ä
/
CHÃ
/
CH2), 101.99, 101.59, 101.34, 101.19, 100.79,
100.59, 94.27 (7 s, 7 C, C-1IꢀVII), 85.42, 84.52, 83.42,
82.30 (4 s, 4 C, C-3IꢀIV), 63.10, 63.09, 62.66, 62.15, 61.98
(5 s, 5 C, C-6II,III,VꢀVII), 22.66, 20.68, 20.64, 20.40 (4 s, 4
C, 4 CH3CO). Anal. Calcd for C165H148O56: C, 65.47;
H, 4.93. Found: C, 65.66; H, 5.01.
col. 1996, 18, 211ꢀ
3. (a) Norisue, T.; Yanaki, T.; Fujita, H. J. Polym. Sci. 1980,
18, 547ꢀ552;
(b) Kojima, T.; Tabata, K.; Itoh, W.; Yanaki, T. Agric.
Biol. Chem. 1986, 50, 231ꢀ238;
(c) Brown, G. D.; Gordon, S. Nature 2001, 413, 36ꢀ
(d) Willment, J. A.; Gordon, S.; Brown, G. D. J. Biol.
Chem. 2001, 276, 43818ꢀ43823;
/
216.
/
/
/37;
3.24. Allyl b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
D
-glucopyranosyl-(10
/
3)-[b-
-glucopyranosyl-(10
-glucopyranosyl-(103)-[b-
6)]-a-D-glucopyranoside (29)
D-
/
/
6)]-b-
D
/
3)-b-
D
-
-
(e) Mueller, A.; Raptis, J.; Rice, P. J.; Kalbfleisch, J. H.;
Stout, R. D.; Ensley, H. E.; Browder, W.; Williams, D. L.
/3)-b-
D
/
D
Glycobiology 2000, 10, 339ꢀ
4. Saito, H.; Ohki, T.; Takasuka, N.; Sasaki, T. Carbohydr.
Res. 1977, 58, 293ꢀ305.
5. Yang, G.; Kong, F. Synlett 2000, 1423ꢀ
6. Ning, J.; Zhang, W.; Yi, Y.; Yang, G.; Wu, Z.; Yi, J.; Kong,
F. Bioorg. Biomed. Chem. 2003, 11, 2193ꢀ2203.
7. Schmidt, R. R.; Kinzy, W. Adv. Carbohydr. Chem. Bio-
chem. 1994, 50, 21ꢀ125.
8. (a) Zeng, Y.; Ning, J.; Kong, F. Tetrahedron Lett. 2002,
3729ꢀ3733;
(b) Zeng, Y.; Ning, J.; Kong, F. Carbohydr. Res. 2003, 338,
307ꢀ311.
/
346.
/
/
A satd soln of NH3 in MeOH (5 mL) was added to a
soln of compound 28 (180 mg, 0.059 mmol) in MeOH (4
mL). After 48 h at rt, the reaction mixture was
concentrated, and the residue was purified by Sephadex
/1426.
/
LH-20 chromatography (MeOH) to afford 29 (70 mg,
/
1
98%): [a]2D0
ꢁ
/
4.38 (c, 1.0, H2O); H NMR d: 6.06ꢀ
/
5.96
5.37 (m, 2 H, CH2Ä
), 4.98 (d, 1 H, J1,2 3.6 Hz, H-1I), 4.76, 4.76,
4.75, 4.53, 4.50, 4.50 (6 d, 6 H, J 8.0 Hz, H-1IIꢀVII),
(m, 1 H, CH2Ä
/
CH Ã
/
CH2Ã
/
), 5.42ꢀ
/
/
/
CHÃCH2Ã
/
/
/