Highly efficient synthesis of alternate α- and β-(1→ 3)-linked glucose hepta- and octasaccharides

Article abstract of DOI:10.1016/S0008-6215(03)00353-7

Two heptasaccharides α-D-Glcp-(1→3)-β-D-Glcp-(1→ 3)-α-D-Glcp-(1→3)-β-D-Glcp-(1→3)-α-D-Glcp-(1→3) -β-D-Glcp-(1→3)-β-D-Glcp-1-OMP and β-D-Glcp-(1→ 3)-α-D-Glcp-(1→3)-β-D-Glcp-(1→3)-α-D-Glcp-(1→3) -β-D-Glcp-(1→3)-α-D-Glcp-(1→3)-β-D-Glcp1-OMP, and two octasaccharides α-D-Glcp-(1→3)-β-D-Glcp-(1→3)-α -D-Glcp-(1→3)-β-D-Glcp-(1→3)-α-D-Glcp-(1→3) -β-D-Glcp-(1→3)-α-D-Glcp-(1→3)-β-D-Glcp-1-OMP and β-D-Glcp-(1→3)-α-D-Glcp-(1→3)-β-D-Glcp-(1→3) -α-D-Glcp-(1→3)-β-D-Glcp-(1→3)-α-D-Glcp-(1→3) -β-D-Glcp-(1→3)-β-D-Glcp1-OMP were synthesized in a stereospecific way by remote control.

Full text of DOI:10.1016/S0008-6215(03)00353-7

Carbohydrate Research 338 (2003) 2047ꢀ2056
/
www.elsevier.com/locate/carres
Highly efficient synthesis of alternate a- and b-(10
/
3)-linked glucose
hepta- and octasaccharides
Ying Zeng, Fanzuo Kong*
Research Center for Eco-Environmental Sciences, Academia Sinica, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085, PR China
Received 29 May 2003; accepted 12 July 2003
Abstract
Two heptasaccharides a-
-Glcp-1-OMP and b- -Glcp-(10
-Glcp1-OMP, and two octasaccharides a-
-Glcp-(103)-a- -Glcp-(103)-b-
3)-a- -Glcp-(103)-b- -Glcp-(10
# 2003 Elsevier Ltd. All rights reserved.
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-
b-
D
D
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
/
D
/
D
-Glcp-1-OMP and b-
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D
-Glcp-(10
/
3)-a-
D
-Glcp-(10
/
3)-b-
D-
Glcp-(10
/
D
/
D
/
D-Glcp1-OMP were synthesized in a stereospecific way by remote control.
Keywords: Oligosaccharide; Glucose; Stereoselective synthesis
1. Introduction
bioactivity studies. Our previous communications6 dis-
closed a new method for construction of glucose
b-
some biologically important natural products, such as
D
-(10
/
3)-Linked glucans are widely distributed in
oligosaccharides with alternate a- and b-(10
/
3) linkages
by remote stereocontrol. We present herein the synthesis
of glucose hepta- and octasaccharides with alternate a-
Ganoderma lucidum, Schizophyllum commune and Len-
3)-Linked glucans are found from
tinus edodes.1 a-(10
/
and b-, or alternate b- and a-(10
/3) linkages.
some fungi such as Cryphonectrini parasitica and
Ganoderma lucidum.2 Although these glucans have
high molecular weight, their active fragments are usually
2. Results and discussion
Our previous report revealed that in (103)-glucosylation
oligosaccharides with DP 6ꢀ
7.3 In order to investigate
the relationship between structure and function of these
/
/
the glycosyl bond originally present in either donor or
acceptor control the stereoselectivity of the forthcoming
bond, i.e., the newly formed glycosidic linkage has the
opposite anomeric configuration of that of either the
donor or acceptor in spite of the presence of a C-2 ester
capable of neighboring group participation. Thus, con-
oligosaccharides, a series of model compounds including
artificially designed structures, are needed. The b-(10
/
3)-linked glucose oligosaccharides have been obtained
by synthesis4a and from degradation of curdlan,4b and
the bioactivity of sulfated oligosaccharides has been
tested.4b,4c The synthesis of an a-(10
/
3)-linked glucose
polysaccharide5a has been reported, and the bioactivity
of a sulfated a-(103)-linked glucan as a potential
antitumor agent has also been evaluated.5b Glucans
with alternate a- and b-(103) linkages are novel
molecules that will be useful in conformation and
densation of an a-(10
ana-(103)-linkeddisaccharideacceptorreadilyaffordsa
b-linked tetrasaccharide. Meanwhile, coupling of a b-
3)-linked
/
3)-linked disaccharide donor with
/
/
(10
/
3)-linked disaccharide donor with a b-(10
/
/
disaccharide acceptor, gives an a-linked tetrasaccharide.
Based on the previously reported method, a glucose
heptasaccharide with alternate a- and b-(10
was prepared as outlined in Scheme 1. Condensation of
2,4,6-tri-O-acetyl-3-O-allyl-a- -glucopyranosyl-(103)-
2,4,6-tri-O-acetyl-a- -glucopyranosyl trichloroacetimi-
/
3) linkages
* Corresponding author. Tel.: ꢁ
10-62923563.
E-mail address: fzkong@mail.rcees.ac.cn (F. Kong).
/
86-10-62936613; fax: ꢁ86-
/
D
/
D
0008-6215/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0008-6215(03)00353-7

2048
Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ2056
/
Scheme 1. Reagents and conditions: (a) TMSOTf, CH2Cl2, ꢂ
/
20 8C to rt. (b) PdCl2, MeOH, rt, 3 h. (c) Satd NH3ꢀMeOH, rt, 7
/
days.
date (1)6b with the trisaccharide acceptor 2, obtained by
deallylation of 4-methoxyphenyl 2,4,6-tri-O-acetyl-3-O-
acetyl-a-
D
-glucopyranosyl trichloroacetimidate (8)6b
-glucopyr-
with 4-methoxyphenyl 2,4,6-tri-O-acetyl-b-
D
allyl-a-
D
-glucopyranosyl-(10
/
3)-2,4,6-tri-O-acetyl-b-
D
-
anoside, followed by deallylation. Again, a-linked
pentasaccharide 10 was obtained stereospecifically in
good yield (73%) in spite of the presence of the C-2 ester
group in the donor. Deallylation of 10 (82%), followed
by reaction with the disaccharide donor 12,6a also gave
the a-linked heptasaccharide 13 (66%), and subsequent
deacylation afforded the target glucoheptaose with
glucopyranosyl-(10
/
3)-2,4,6-tri-O-acetyl-b-
D
-glucopyr-
anoside,6b stereospecifically gave a b-linked pentasac-
charide 3 in high yield (84%). Deallylation of 3 with PdCl2
in methanol was carried out smoothly affording the
pentasaccharide acceptor 4 (85%). Coupling of the donor
1 with the acceptor 4 yielded a b-linked heptasaccharide 5
in satisfactory yield (76%). Deallylation of 5 furnished 6
(87%) and subsequent deacetyaltion in saturated
alternate b- and a-(10
Syntheses of the glucooctaose 19 with alternate a- and
b-(103)-bonds and the glucooctaose 24 with alternate
b- and a-(103)-bonds are shown in Schemes 3 and 4,
/
/3)-bonds.
ammoniaꢀ/methanol solution quantitatively gave the
/
glucoheptaose 7 with alternate a- and b-(10
/
3) linkages.
/
The H and 13C NMR spectra of 7 showed all of the
characteristic signals such as d 5.24, 5.24 and 5.21 (J1,2 3.2
or 4.0 Hz) for H-1 (a), and d 4.88, 4.69, 4.67 and 4.61 (J1,2
7.6 Hz) for H-1 (b), and d 101.21, 101.08 and 101.08 for C-
1(a), and d 104.97, 104.97, 104.97 and 103.15 for C-1(b).
Scheme 2 shows the synthesis of the frame-shifted
respectively. For the former, alternately a- and b-(10
1
3)-linked hexasaccharide (15)6b was deallylated to give
the acceptor 16 (81%). Coupling of 16 with 1 stereo-
specifically furnished b-linked octasaccharide 17 (77%).
Deallylation to give 18 (85%), followed by deacetylation,
yielded the target glucooctaose 19. For the latter,
heptasaccharide 14 with alternate b- and a-(10
/
3)
condensation of 8 with the alternate b- and a-(10
linked glucotetraose acceptor, which was prepared from
deallylation of the corresponding glucotetraose,6b af-
/
3)-
linkages. In this synthesis, a b-(10
/
3)-linked disacchar-
ide trichloroacetimidate 86b was used as the glycosyl
donor, and a trisaccharide 9 was used as the acceptor,
which was prepared by condensation of 2,4,6-tri-O-
forded the alternate b- and a-(10/3)-linked glucohex-
aose 21 (79%). Deallylation, followed by coupling with
the disaccharide donor 12, and subsequent deacylation
acetyl-3-O-allyl-b-
D
-glucopyranosyl-(10
/
3)-2,4,6-tri-O-

Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ
/
2056
2049
Scheme 2. Reagents and conditions: (a) TMSOTf, CH2Cl2, ꢂ
/
20 8C to rt. (b) PdCl2, MeOH, rt, 3 h. (c) Satd NH3ꢀ
/MeOH, rt, 7
days.
Scheme 3. Reagents and conditions: (a) TMSOTf, CH2Cl2, ꢂ
/
20 8C to rt. (b) PdCl2, MeOH, rt, 3 h. (c) Satd NH3ꢀ
/MeOH, rt, 7
days.

2050
Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ2056
/
Scheme 4. Reagents and conditions: (a) TMSOTf, CH2Cl2, ꢂ
/
20 8C to rt. (b) PdCl2, MeOH, rt, 3 h. (c) Satd NH3ꢀMeOH, rt, 7
/
days.
gave the target glucooctaose 24 with alternate b- and a-
meter using the ESI mode. Thin-layer chromatography
(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 was conducted by
(10/3)-bonds.
For investigation of the antiviral activities, 7 and 14
were sulfated. The biological evaluations of all of the
hepta- and octaoses are in progress.
elution of a column (8ꢃ
400 mm) of silica gel (100ꢀ
petroleum ether (bp 60ꢀ90 8C) as the eluent. Analytical
/
100, 16ꢃ
/
240, 18ꢃ
/
300, 35ꢃ
/
In summary, alternate a- and b-(10
/
3)-linked and b-
/
200 mesh) with EtOAcꢀ
/
and a-(103)-linked glucoheptaoses and glucooctaoses
/
/
were readily synthesized in a stereospecific manner by
remote stereocontrol. Owing to the use of acyl groups in
the syntheses, the procedure was significantly simplified,
and large-scale preparations of higher oligosaccharides
should be possible.
LC was performed with a Gilson HPLC consisting of a
pump (model 306), stainless steel column packed with
silica gel (Spherisorb SiO2, 10ꢃ
differential refractometer (132-RI Detector), UVꢀ
detector (model 118). EtOAcꢀpetroleum ether (bp 60ꢀ
90 8C) was used as the eluent at a flow rate of 1ꢀ4 mL/
min. Solutions were concentrated at a temperature B
/
300 or 4.6ꢃ
/
250 mm),
/
Vis
/
/
/
/
60 8C under diminished pressure.
3. Experimental
3.1. General methods
3.2. General procedure for deallylation7 to prepare
acceptors
Melting points were determined with a ‘Mel-Temp’
apparatus. Optical rotations were determined with a
Perkinꢀ
/
Elmer model 241-MC automatic polarimeter for
To a solution of 3-O-allylated oligosaccharide [3, 5, 10,
0.124 mmol)] in MeOH was added
solutions in a 1-dm, jacketed cell. H NMR, 13C NMR,
and 2D NMR spectra were recorded with Varian XL-
400 spectrometers, for solutions in CDCl3 or in D2O as
indicated. Chemical shifts are expressed in d (ppm)
downfield from the Me4Si absorption. Mass spectra
were recorded with a VG PLATFORM mass spectro-
15, 17 or 21 (0.387ꢀ
/
1
PdCl2 (60ꢀ20 mg). After stirring for several h at room
/
temperature (rt), TLC indicated that the reaction was
complete. The mixture was filtered, and the combined
filtrate and washings were concentrated to dryness. The
resultant residue was purified by flash chromatography

Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ
/
2056
2051
to give products [4, 6, 11, 16, 18 or 22 (81ꢀ
respectively.
/
87%)],
2.07, 2.07, 2.06, 2.05 (9 CH3CO). Anal. Calcd for
C43H56O26: C, 52.23; H, 5.71. Found: C, 52.34; H, 5.74.
3.3. General procedure for the glycosidation8
3.7. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-3-O-allyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (3)
D-
The mixture of donor (1, 8 or 12) and acceptor (2, 4, 9,
11, 16, 20 or 22) was dried together under high vacuum
for 2 h, then dissolved in anhyd CH2Cl2. TMSOTf (0.05
/
D-
/
D
-
-
-
/
3)-2,4,6-tri-O-acetyl-b-
D
equiv) was added dropwise at ꢂ20 8C with N2 protec-
/
/
3)-2,4,6-tri-O-acetyl-b-
D
tion. 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, gave
the corresponding products (3, 5, 10, 13, 17, 21 or 23).
Donor 1 (245 mg, 0.314 mmol) was coupled with
acceptor 2 (310 mg, 0.314 mmol) to give 3 (420 mg,
84%): [a]D
CDCl3): d 6.92ꢀ
1 H, ÃCH ꢀ), 5.22ꢀ
Hz, b H-1), 4.71ꢀ4.57 (m, 2 H), 4.49 (d, 1 H, J 8.0 Hz, b
H-1), 4.45 (d, 1 H, J 8.0 Hz, b H-1), 4.29ꢀ3.82 (m, 18
H), 3.79ꢀ3.77 (m, 4 H, CH3O), 3.68 (dd, 1 H, J 9.2 Hz),
3.58ꢀ3.53 (m, 2 H), 2.15, 2.14, 2.11, 2.10, 2.08, 2.07,
ꢂ
/
17.38(c 1.5, H CCl3); 1H NMR (400 MHz,
/
6.79 (dd, 4 H, Ã
/
C6H4Ã
/
), 5.80ꢀ5.74 (m,
/
/
/
/
4.98 (m, 12 H), 4.81 (d, 1 H, J 8.0
3.4. General procedure for the deacylation
/
/
The oligosaccharides (6, 13, 18 or 23) was added to a
saturated solution of NH3 in MeOH (40 mL). After a
week at rt, the reaction mixture was concentrated, and
the residue was purified by chromatography on a
/
/
2.07, 2.07, 2.07, 2.05, 2.04, 2.03, 2.02, 1.97 (15 CH3CO
some signals overlapped); 13C NMR (100 MHz, CDCl3):
d 170.54, 170.52, 170.50, 170.39, 170.30, 169.35, 169.11,
169.09, 168.91, 168.85, 168.62, 168.59, 166.99 (15
CH3CO some signals overlapped), 155.65, 150.85,
Sephadex LH-20 (column 2.0ꢃ30 cm, flow 5 mL/min,
/
about 300 mL MeOH) to afford the products as a white
amorphous powder (7, 14, 19 or 24), respectively.
3.5. General procedure for sulfation4c
134.20, 118.38, 116.64, 114.46 (CH2ꢀ
/
CHÃ
/
CH2Ã
/,
MeOPh), 100.67 (b C-1), 100.58 (b C-1), 100.04 (b C-
1), 95.87 (a C-1), 94.91 (a C-1), 78.21, 75.91, 74.93,
74.89, 73.84, 73.03, 72.68, 72.31, 71.92, 71.72, 71.56,
71.13, 70.49, 69.71, 69.18, 68.31, 68.13, 67.83, 67.38,
62.13, 61.44, 55.55, 51.98, 20.88, 20.85, 20.76, 20.69,
20.66, 20.64, 20.58, 20.56, 2.50, 20.45, 20.34 (some
signals overlapped). Anal. Calcd for C70H92O42: C,
52.37; H, 5.78. Found: C, 52.28; H, 5.71.
The free oligosaccharide (7 or 14) was dissolved in
pyridine at 85 8C, and SO3ꢀpyridine complex (500 mg)
/
was added, with subsequent stirring for 90 min. After
cooling at rt, the solution was adjusted with satd
Ba(OH)2 to pH 8.0 in an ice bath. The BaSO4 was
separated by centrifugation, and water was evaporated
off. The residue was passed through a Naꢁ type ion-
exchange resin column. The product was precipitated
with acetone.
3.8. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (4)
D-
3.6. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-a-D-
/
D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (2)
/
3)-2,4,6-tri-O-acetyl-b-
D
-
-
/
D
-
-
-
/
3)-2,4,6-tri-O-acetyl-b-
D
/
3)-2,4,6-tri-O-acetyl-b-
D
/
3)-2,4,6-tri-O-acetyl-b-
D
Deallylation of 4-methoxyphenyl 2,4,6-tri-O-acetyl-3-
O-allyl-a- -glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
-glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b- -gluco-
pyranoside (400 mg, 0.387 mmol) gave acceptor 2 (324
D
/
Deallylation of 3 (400 mg, 0.25 mmol) gave acceptor 4
D
/
D
1
(330 mg, 85%): [a]D
(400 MHz, CDCl3): d 6.92ꢀ
5.20 (d, 1 H, J 4.0 Hz, a H-1), 5.19 (dd, 1 H, J 8.0 Hz),
5.16ꢀ4.87 (m, 8 H), 4.84 (d, 1 H, J 8.0 Hz, b H-1), 4.71ꢀ
4.59 (m, 2 H), 4.49 (d, 1 H, J 8.0 Hz, b H-1), 4.46 (d, 1
H, J 8.0 Hz, b H-1), 4.32ꢀ3.87 (m, 17 H), 3.79ꢀ3.77 (m,
4 H, CH3O), 3.58ꢀ3.53 (m, 2 H), 2.15, 2.14, 2.13, 2.11,
ꢂ
/
10.88 (c 1.5, HCCl3); H NMR
1
/
6.79 (dd, 4 H, ÃC6H4Ã),
/
/
mg, 84%): [a]D
ꢂ
/
24.58 (c 1.5, HCCl3); H NMR (400
MHz, CDCl3): d 6.93ꢀ
/
6.80 (dd, 4 H, ÃC6H4Ã), 5.23 (d,
/
/
/
/
1 H, J 3.6 Hz, a H-1), 5.20 (dd, 1 H, J 9.2 Hz), 5.18 (dd,
1 H, J 9.6 Hz), 5.00 (d, 1 H, J 9.6 Hz), 4.97 (dd, 1 H, J
9.6 Hz), 4.91 (dd, 1 H, J 9.6 Hz), 4.81 (d, 1 H, J 8.0 Hz,
/
/
/
b H-1), 4.61 (dd, 1 H, J1,2 3.6, J
9.6 Hz, H-2ƒ), 4.49
/
3,4
2.09, 2.08, 2.07, 2.05, 2.03, 2.02, 1.98 (15 CH3CO some
signals overlapped). Anal. Calcd for C67H88O42: C,
51.41; H, 5.67. Found: C, 51.52; H, 5.56.
(d, 1 H, J 8.0 Hz, b H-1), 4.31ꢀ
(m, 7 H), 3.84 (dd, 1 H, J 9.6 Hz), 3.81ꢀ
CH3O), 3.57ꢀ3.55 (m, 1 H), 2.15, 2.12, 2.10, 2.10, 2.09,
/
4.25 (m, 2 H), 4.20ꢀ
3.90
/3.77 (m, 4 H,
/

2052
Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ2056
/
3.9. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-3-O-allyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (5)
D
-
3.11. 4-Methoxyphenyl a-
D
-glucopyranosyl-(10
/
3)-b-D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
/
3)-a-
D
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranoside (7)
/
3)-b-
D
-
-
/
D-
/3)-a-
D
/3)-b-
D
/
D-
/3)-b-
D
/
3)-2,4,6-tri-O-acetyl-b-
D-
/
3)-2,4,6-tri-O-acetyl-a-
D
-
-
-
Compound 7 (140 mg) was obtained by deacetylation of
/
3)-2,4,6-tri-O-acetyl-b-
D
1
6 (255 mg, 0.120 mmol): [a]D
NMR (400 MHz, D2O): d 6.99ꢀ
C6H4Ã), 5.24 (d, 2 H, J 3.2 Hz, 2a H-1), 5.21 (d, 1 H,
J 4.0 Hz, a H-1), 4.88 (d, 1 H, J 7.6 Hz, b H-1), 4.69ꢀ
4.66 (m, 2 H, 2 b H-1), 4.61 (d, 1 H, J 7.6 Hz, b H-1),
3.97ꢀ
3.27 (m, 45 H); 13C NMR (100 MHz, D2O): d
ꢂ
/
0.48(c 1.0, H2O); H
/
3)-2,4,6-tri-O-acetyl-b-
D
/
6.82 (dd, 4 H, Ã
/
/
/
Donor 1 (155 mg, 0.198 mmol) was coupled with
acceptor 4 (310 mg, 0.198 mmol) to give 5 (328 mg,
1
/
76%): [a]D
CDCl3): d 6.91ꢀ
1 H, ÃCH ꢀ), 5.21ꢀ
Hz, b H-1), 4.71ꢀ4.68 (m, 3 H), 4.50ꢀ
4.32ꢀ3.82 (m, 25 H), 3.81ꢀ3.71 (m, 4 H, CH3O), 3.56
(dd, 1 H, J 9.0 Hz), 3.56ꢀ3.54 (m, 3 H), 2.15, 2.14, 2.14,
ꢂ
/
8.78 (c 1.5, H CCl3); H NMR (400 MHz,
156.87, 153.00, 120.40, 117.16 (MeOPh), 104.97 (b C-1),
104.97 (b C-1), 104.97 (b C-1), 103.15 (b C-1), 101.21 (a
C-1), 101.08 (a C-1), 101.08 (a C-1), 86.36, 84.29, 84.06,
75.55, 75.31, 75.03, 74.83, 74.33, 73.85, 73.62, 73.30,
72.93, 72.39, 72.13, 72.07, 71.88, 71.68, 71.42, 71.22,
71.01, 70.80, 70.24, 70.09, 70.9, 70.63, 62.35, 57.90
(some signals overlapped). Anal. Calcd for C49H78O37:
C, 46.74; H, 6.24. Found: C, 46.92; H, 6.21.
/
6.79 (dd, 4 H, Ã
4.93 (m, 16 H), 4.81 (d, 1 H, J 8.0
4.43 (m, 3 H),
/
C6H4Ã
/
), 5.80ꢀ
/
5.73 (m,
/
/
/
/
/
/
/
/
2.11, 2.10, 2.10, 2.10, 2.09, 2.09, 2.07, 2.07, 2.07, 2.06,
2.04, 2.04, 2.03, 2.02, 2.01, 2.01, 1.97, 1.96 (18 s, 18
CH3CO); 13C NMR (100 MHz, CDCl3): d 170.70,
170.68, 170.65, 170.50, 170.45, 169.53, 169.49, 169.24,
169.18, 169.05, 168.99, 16.875, 168.59 (18 CH3CO, some
signals overlapped), 155.67, 150.45, 134.38, 118.57,
Sulfation of 7 (120 mg, 0.0985 mmol) gave sulfated
oligosaccharide (170 mg): 1H NMR (400 MHz, D2O): d
7.11ꢀ
1), 5.29 (d, 1 H, J 5.6 Hz, b H-1), 5.09ꢀ
H-1), 4.87ꢀ
4.13 (m, 42 H), 3.74 (s, 3 H, CH3O); 13C
/
6.89 (dd, 4 H, Ã
/
C6H4Ã
/
), 5.66ꢀ
/
5.63 (m, 3 H, 3 a H-
/
5.08 (m, 3 H, 3 b
/
116.78, 114.65 (CH2ꢀ
/
CHÃ
/
CH2Ã, MeOPh), 100.82 (b
/
NMR (100 MHz, D2O): d 158.84, 154.86, 118.71, 115.23
(MeOPh), 100.26 (b C-1), 99.80 (3 b C-1), 95.31 (a C-1),
95.20 (a C-1), 95.15 (a C-1), 78.59, 78.36, 78.04, 76.49,
76.36, 75.99, 75.31, 75.02, 74.81, 74.59, 74.35, 74.04,
73.29, 73.67, 68.91, 68.66, 68.37, 68.20, 67.87, 67.66,
66.63, 66.37, 56.08 (some signals overlapped). Anal.
Found (Calcd): C, 14.10 (16.8); H, 2.38 (1.60); S, 16.63
(20.11). The degree of sulfation (ds) 2.2 (ds designate the
number of sulfate groups per glucose residue).
C-1), 100.76 (b C-1), 100.65 (b C-1), 100.22 (b C-1),
96.01 (a C-1), 95.21 (a C-1), 95.06 (a C-1), 78.36, 76.11,
75.58, 75.09, 75.01, 74.93, 74.00, 73.18, 72.90, 72.46,
72.13, 71.87, 71.76, 71.49, 71.32, 70.73, 69.98, 69.37,
68.49, 68.36, 68.07, 68.01, 67.59, 62.33, 62.02, 61.67,
55.74, 21.01, 20.92, 20.82, 20.73, 20.66, 20.62, 20.52
(some signals overlapped). Anal. Calcd for C94H124O58:
C, 51.74; H, 5.73. Found: C, 51.62; H, 5.80.
3.12. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranoside (9)
D-
3.10. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-a-D-
/
D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (6)
/
3)-2,4,6-tri-O-acetyl-b-
D-
/
D-
/
3)-2,4,6-tri-O-acetyl-a-
D-
/
3)-2,4,6-tri-O-acetyl-b-
D
-
/
3)-2,4,6-tri-O-acetyl-a-
D
-
-
-
Deallylation of 4-methoxyphenyl 2,4,6-tri-O-acetyl-3-
O-allyl-b- -glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a-
-glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b- -gluco-
pyranoside (400 mg, 0.387 mmol) gave acceptor 9 (385
/
3)-2,4,6-tri-O-acetyl-b-
D
D
/
/
3)-2,4,6-tri-O-acetyl-b-
D
D
/
D
1
mg, 87%): [a]D
ꢁ
/
5.78 (c 1.5, HCCl3); H NMR (400
Deallylation of 5 (300 mg, 0.138 mmol) gave 6 (256 mg,
MHz, CDCl3): d 6.93ꢀ
/
6.80 (dd, 4 H, ÃC6H4Ã), 5.27
/
/
1
87%): [a]D
CDCl3): d 6.91ꢀ
14 H), 4.81 (d, 1 H, J 8.0 Hz, b H-1), 4.71ꢀ
H), 4.62ꢀ4.59 (m, 1 H), 4.50ꢀ4.43 (m, 3 H), 4.30ꢀ
(m, 23 H), 3.81ꢀ3.71 (m, 5 H, CH3O), 3.57ꢀ3.55 (m, 3
ꢂ
/
7.68 (c 1.5, H CCl3); H NMR (400 MHz,
6.79 (dd, 4 H, ÃC6H4Ã), 5.20ꢀ4.89 (m,
4.68 (m, 2
3.79
(dd, 1 H, J 9.2 Hz), 5.28 (dd, 1 H, J 9.6 Hz), 5.20 (d, 1
H, J 3.2 Hz, a H-1), 4.99 (dd, 1 H, J 9.6 Hz), 4.90 (dd, 1
H, J 9.6 Hz), 4.82 (d, 1 H, J 8.0 Hz, b H-1), 4.80 (dd, 1
H, J1,2 4.0, J3,4 9.6 Hz, H-2?), 4.71 (dd, 1 H, J 9.6 Hz),
/
/
/
/
/
/
/
/
/
/
4.58 (d, 1 H, J 8.0 Hz, b H-1), 4.41ꢀ
/
4.21 (m, 2 H), 4.18ꢀ
/
H), 2.15, 2.14, 2.14, 2.12, 2.11,, 2.10, 2.09, 2.09, 2.09,
2.07, 2.07, 2.07, 2.06, 2.04, 2.04, 2.03, 2.02, 2.01, 2.01,
1.98, 1.95 (18 s, 18 CH3CO). Anal. Calcd for
C91H120O58: C, 51.03; H, 5.65. Found: C, 50.93; H, 5.68.
3.99 (m, 7 H), 3.77 (s, 3 H, CH3O), 3.72ꢀ
/3.52 (m, 3 H),
2.20, 2.10, 2.10, 2.09, 2.09, 2.07, 2.06, 2.04, 2.02 (9
CH3CO). Anal. Calcd for C43H56O26: C, 52.23; H, 5.71.
Found: C, 52.26; H, 5.74.

Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ
/
2056
2053
3.13. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-3-O-allyl-b-
D-
3.15. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (10)
/
3)-2,4,6-tri-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
D
-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (13)
/
3)-2,4,6-tri-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
D
-
/
D-
/
D-
/
D-
/
D-
/
D-
/
3)-2,4,6-tri-O-acetyl-b-
D
-
/
3)-2,4,6-tri-O-acetyl-a-
D-
/
3)-2,4,6-tri-O-acetyl-b-
D
-
Donor 8 (245 mg, 0.314 mmol) was coupled with
acceptor 9 (360 mg, 0.314 mmol) to give 10 (426 mg,
1
73%): [a]D
CDCl3): d 6.92ꢀ
1 H, ÃCH ꢀ), 5.26ꢀ
Hz), 4.81 (d, 1 H, J 7.8 Hz, b H-1), 4.73ꢀ
4.51 (d, 1 H, J 8.2 Hz, b H-1), 4.48 (d, 1 H, J 8.2 Hz, b
H-1) 4.31ꢀ3.85 (m, 18 H), 3.77 (s, 3 H, CH3O), 3.69ꢀ
ꢁ
/
8.78 (c 1.0, HCCl3); H NMR (400 MHz,
Donor 12 (200 mg, 0.191 mmol) was coupled with
acceptor 11 (300 mg, 0.191 mmol) to give 13 (335 mg,
/
6.80 (dd, 4 H, Ã
4.93 (m, 11 H), 4.86 (dd, 1 H, J 9.2
4.69 (m, 2 H),
/
C6H4Ã
/
), 5.76ꢀ
/
5.69 (m,
1
/
/
/
66%): [a]D
CDCl3): d 7.87ꢀ
4 H, ÃC6H4Ã), 5.90 (dd, 1 H, J 9.6 Hz), 5.70 (dd, 1 H, J
9.6 Hz), 5.36 (dd, 1 H, J 9.6 Hz), 5.26ꢀ4.87 (m, 14 H),
4.80 (d, 1 H, J 8.0 Hz, b H-1), 4.72ꢀ4.69 (m, 3 H), 4.57ꢀ
4.41 (m, 4 H), 4.30ꢀ3.82 (m, 20 H), 3.79ꢀ3.77 (m, 4 H,
CH3O), 3.70ꢀ3.48 (m, 3 H), 2.16, 2.12, 2.09, 2.08, 2.04,
ꢁ
/
5.78 (c 1.0, CCl3H); H NMR (400 MHz,
/
/
7.34 (m, 20 H, 4 PhCO), 6.91ꢀ6.18 (dd,
/
/
/
/
/
/
3.48 (m, 4 H), 2.16, 2.16, 2.10, 2.09, 2.09, 2.06, 2.05,
2.04, 2.03, 2.00, 1.99, 1.97 (15 CH3CO some signals
overlapped); 13C NMR (100 MHz, CDCl3): d 170.63,
170.54, 170.46, 170.40, 170.37, 170.26, 169.37, 169.15,
168.90, 168.81, 168.67, 168.43 (15 CH3CO some signals
overlapped), 155.76, 150.85, 134.03, 118.49, 116.75,
/
/
/
/
/
2.01, 1.96, 1.93, 1.88, 1.85 (18 CH3CO some signals
overlapped); 13C NMR (100 MHz, CDCl3): d 170.51,
170.47, 170.43, 170.40, 170.26, 169.99, 169.37, 169.25,
169.06, 168.93, 168.82, 168.67, 168.47 (18 CH3CO some
signals overlapped), 165.96, 165.79, 164.91 (4 PhCO
some signals overlapped), 155.54, 150.87, 118.47, 114.47
(MeOPh), 101.09 (b C-1), 100.44 (3 b C-1), 95.33 (a C-
1), 95.23 (a C-1), 95.03 (a C-1), 76.33, 75.39, 5.07, 74.93,
74.82, 74.45, 73.08, 72.72, 72.34, 71.92, 71.88, 71.61,
71.55, 71.48, 71.30, 70.37, 70.29, 69.71, 69.16, 68.42,
67.91, 67.86, 67.40, 67.32, 62.55, 61.75, 61.39, 55.53,
21.04, 20.84, 20.79, 20.70, 20.65, 20.57, 20.52, 20.46,
20.39, 20.35 (some signals overlapped). Anal. Calcd for
114.49 (CH2ꢀ
/
CHÃ
/
CH2Ã, MeOPh), 100.78 (b C-1),
/
10047 (b C-1), 100.47 (b C-1), 9525 (a C-1), 95.10 (a
C-1), 75.33, 75.10, 74.95, 74.80, 72.35, 72.23, 72.14,
72.05, 71.57, 71.44, 71.22, 70.37, 69.10, 67.93, 67.86,
67.49, 67.43, 61.78, 61.67, 61.43, 55.55, 20.84, 20.79,
20.69, 20.58, 20.47, 20.36 (some signals overlapped)
Anal. Calcd for C70H92O42: C, 52.37; H, 5.78. Found: C,
52.43; H, 5.81.
3.14. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
D
-
C113H130O59: C, 55.80; H, 5.39. Found: C, 55.97; H,
5.31.
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (11)
/
D-
/
3)-2,4,6-tri-O-acetyl-b-
D
-
-
-
/
3)-2,4,6-tri-O-acetyl-a-
D
3.16. 4-Methoxyphenyl b-
D
-glucopyranosyl-(10
/
3)-a-D-
/
3)-2,4,6-tri-O-acetyl-b-
D
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
/
3)-b-
3)-b-
3)-b-
D
D
D
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranoside (14)
/
3)-a-
D
-
-
/
/3)-a-D
/
Deallylation of 10 (400 mg, 0.387 mmol) gave acceptor
11 (320 mg, 82%): [a]D ꢁ
11.38 (c 1.0, HCCl3); 1H NMR
(400 MHz, CDCl3): d 6.91ꢀ6.78 (dd, 4 H, ÃC6H4Ã),
5.24ꢀ4.87 (m, 10 H), 4.80 (d, 1 H, J 7.8 Hz, b H-1),
4.76ꢀ4.68 (m, 2 H), 4.50 (d, 2 H, J 8.2 Hz, 2 b H-1),
4.33ꢀ3.85 (m, 14 H), 3.77 (s, 3 H, CH3O), 3.69ꢀ3.56 (m,
4 H), 2.15, 2.15, 2.08, 2.05, 2.04, 2.02, 2.01, 2.00, 1.96,
1.91 (15 CH3CO some signals overlapped); 13C NMR
(100 MHz, CDCl3): d 170.59, 170.55, 170.48, 170.43,
170.38, 170.26, 169.38, 169.32, 169.08, 168.93, 168.83,
168.48 (15 CH3CO some signals overlapped), 155.73,
150.83, 118.46, 114.47 (MeOPh), 100.44 (3 b C-1), 95.26
(a C-1), 95.2 (a C-1), 75.64, 75.07, 75.03, 74.06, 74.02,
72.35, 72.19, 71.87, 71.69, 71.54, 71.50, 71.31, 70.49,
70.37, 70.25, 67.90, 67.41, 67.32, 61.74, 61.40, 20.88,
20.84, 20.78, 20.65, 20.60, 20.57, 20.52, 20.43, 20.35,
20.29 (some signals overlapped). Anal. Calcd for
C67H88O42: C, 51.41; H, 5.67. Found: C, 51.55; H, 5.86.
/
Compound 14 (140 mg) was obtained by deacylation of
1
/
/
/
13 (335 mg, 0.125 mmol): [a]D
NMR (400 MHz, D2O): d 6.96ꢀ
C6H4Ã), 5.23 (s, 3 H, 3 a H-1), 4.83 (d, 1 H, J 8.0 Hz,
b H-1), 4.61ꢀ 3.23 (m, 45
ꢂ
/
2.68 (c 0.5, H2O); H
/
/
6.78 (dd, 4 H, Ã
/
/
/
/
/
/
4.55 (m, 3 H, 3 b H-1), 3.96ꢀ
/
H); 13C NMR (100 MHz, D2O): d 156.79, 153.18,
120.38, 117.11 (MeOPh), 104.96 (b C-1), 104.96 (b C-1),
104.93 (b C-1), 103.52 (b C-1), 101.15 (a C-1), 101.15 (a
C-1), 101.07 (a C-1), 78.04, 77.97, 77.70, 75.52, 74.29,
73.78, 73.59, 73.28, 72.10, 71.95, 71.65, 69.89, 62.78,
62.60, 62.48, 62.33, 57.86 (some signals overlapped).
Anal. Calcd for C49H78O37: C, 46.74; H, 6.24. Found: C,
46.87; H, 6.26.
Sulfation of 14 (120 mg, 0.0985 mmol) gave sulfated
oligosaccharide (167 mg): 1H NMR (400 MHz, D2O): d
7.09ꢀ
/
6.93 (dd, 4 H, Ã
/
C6H4Ã
/
), 5.72 (s, 1 H, a H-1), 5.65
(s, 1 H, a H-1), 5.60 (s, 1 H, a H-1), 5.42 (d, 1 H, J 5.6

2054
Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ2056
/
Hz, b H-1), 5.12ꢀ
/
5.06 (m, 3 H, 3 b H-1), 4.74ꢀ
/
4.08 (m,
169.93, 169.66, 169.55, 169.41, 169.38, 169.26, 169.15,
169.10, 168.95, 168.92, 168.85, 168.60, 168.48 (24
CH3CO some signals overlapped), 155.73, 150.83,
42 H), 3.75 (s, 3 H, CH3O); 13C NMR (100 MHz, D2O):
d 157.49, 153.46, 118.22, 114.55 (MeOPh), 101.68 (b C-
1), 101.58 (b C-1), 100.98 (b C-1), 100.98 (b C-1), 96.65
(a C-1), 96.19 (a C-1), 95.74 (a C-1), 80.22, 79.98, 79.50,
79.10, 78.88, 78.47, 77.64, 77.47, 77.23, 76.89, 76.72,
75.41, 71.63, 71.31, 70.76, 70.35, 69.33, 58.79 (some
signals overlapped). Anal. Found (Calcd): C, 13.57
(16.8); H, 2.29 (1.60); S, 15.36 (20.11), ds: 2.1.
130.07, 118.48, 116.69, 114.46 (CH2ꢀ
/
CHÃ
/
CH2Ã
/,
MeOPh), 100.46 (4 b C-1), 95.84 (a C-1), 95.22 (a C-
1), 95.02 (a C-1), 95.02 (a C-1), 76.05, 75.90, 75.40,
75.24, 75.06, 74.96, 74.76, 73.87, 73.01, 72.26, 71.87,
71.63, 71.52, 71.27, 70.26, 69.67, 69.05, 68.27, 67.84,
67.57, 67.32, 61.42, 61.39, 61.32, 20.88, 20.82, 20.70,
20.48, 20.38 (some signals overlapped). Anal. Calcd for
3.17. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-a-
D
-
C106H140O66: C, 51.54; H, 5.71. Found: C, 51.42; H,
5.57.
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (16)
/
3)-2,4,6-tri-O-acetyl-b-
D
-
-
-
-
/
3)-2,4,6-tri-O-acetyl-a-
D
/
3)-2,4,6-tri-O-acetyl-b-
D
/
3)-2,4,6-tri-O-acetyl-a-
D
3.19. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-a-D-
/
3)-2,4,6-tri-O-acetyl-b-
D
-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (18)
/
3)-2,4,6-tri-O-acetyl-b-
D-
/
3)-2,4,6-tri-O-acetyl-a-
D-
/
3)-2,4,6-tri-O-acetyl-b-
D-
Deallylation of 4-methoxyphenyl 2,4,6-tri-O-acetyl-3-
allyl-a- -glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a- -glucopyr-
anosyl-(103)-2,4,6-tri-O-acetyl-b- -glucopyranosyl-
(103)-2,4,6-tri-O-acetyl-a- -glucopyranosyl-(103)-
2,4,6-tri-O-acetyl-b- -glucopyranoside 15 (400 mg,
0.211 mmol) gave acceptor 16 (315 mg, 81%): [a]D
/
3)-2,4,6-tri-O-acetyl-a-
D-
D
/
D-
/
3)-2,4,6-tri-O-acetyl-b-
D-
/
D
/
3)-2,4,6-tri-O-acetyl-a-
D-
/
D
/
3)-2,4,6-tri-O-acetyl-b-
D-
/
D
/
D
ꢁ
/
Deallylation of 17 (310 mg, 0.126 mmol) gave 18 (260
1
57.78 (c 1.4, CHCl3); H NMR (CDCl3): d 6.92ꢀ
(dd, 4 H, ÃC6H4Ã), 5.33ꢀ4.91 (m, 12 H, 3 a-H-1), 4.83
(d, 1 H, J 8.0 Hz, b H-1), 4.79ꢀ4.61 (m, 3 H), 4.52 (d, 1
H, J 8.4 Hz, b H-1), 4.46 (d, 1 H, J 8.4 Hz, b H-1),
4.37ꢀ3.93 (m, 18 H), 3.90ꢀ3.76 (m, 7 H, CH3O), 3.71ꢀ
/
6.77
1
mg, 85%): [a]D
MHz, CDCl3): d 6.91ꢀ
5.08 (m, 9 H), 4.98ꢀ4.89 (m, 7 H), 4.81 (d, 1 H, J 8.0 Hz,
b H-1), 4.77ꢀ4.69 (m, 3 H), 4.62ꢀ4.59 (m, 4 H, CH3O),
3.71ꢀ3.64 (m, 1 H), 3.62ꢀ3.54 (m, 3 H), 2.17, 2.15, 2.14,
ꢁ
/
62.38 (c 0.8, CHCl3); H NMR (400
/
/
/
/
6.79 (dd, 4 H, ÃC6H4Ã), 5.27ꢀ
/
/
/
/
/
/
/
/
/
/
/
/
3.55 (m, 4 H), 2.15, 2.14, 2.10, 2.09, 2.07, 2.07, 2.06,
2.04, 2.03, 2.02, 1.97, 1.96 (54 H, 18 CH3CO). Anal.
Calcd for C79H104O50: C, 51.19; H, 5.66. Found: C,
51.38; H, 5.84.
2.12, 2.10, 2.09, 2.08, 2.07, 2.05, 2.04, 2.03, 2.02, 2.01,
1.98, 1.97, 1.96 (24 CH3CO some signals overlapped).
Anal. Calcd for C103H136O66: C, 50.91; H, 5.64. Found:
C, 50.89; H, 5.69.
3.18. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-3-O-allyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (17)
/
D-
/
D-
3.20. 4-Methoxyphenyl a-
D
-glucopyranosyl-(10
/
3)-b-D-
/
3)-2,4,6-tri-O-acetyl-b-
D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (19)
/
3)-a-
3)-a-
3)-a-
D
D
D
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranosyl-(10
/
3)-b-
3)-b-
3)-b-
D
-
-
-
/
3)-2,4,6-tri-O-acetyl-a-
D-
/
/
D
D
/
3)-2,4,6-tri-O-acetyl-b-
D-
/
/
/
3)-2,4,6-tri-O-acetyl-a-
D-
/
3)-2,4,6-tri-O-acetyl-b-
D-
Compound 19 (142 mg) was obtained by deacylation of
1
18 (260 mg, 0.107 mmol): [a]D
NMR (400 MHz, D2O): d 6.99ꢀ
C6H4Ã), 5.26ꢀ5.24 (m, 3 H, 3 a H-1), 5.22 (d, 1 H, J
3.6 Hz, a H-1), 4.88 (d, 1 H, J 8.0 Hz, b H-1), 4.64ꢀ4.60
(m, 3 H, 3 b H-1), 3.97ꢀ
3.31 (m, 45 H); 13C NMR (100
ꢁ
/
15.78 (c 1.5, H2O); H
Donor 1 (126 mg, 0.162 mmol) was coupled with
acceptor 16 (300 mg, 0.162 mmol) to give 17 (335 mg,
/
6.83 (dd, 4 H, Ã
/
/
/
66%): [a]D
CDCl3): d 6.93ꢀ
1 H, ÃCH ꢀ), 5.24ꢀ
Hz, b H-1), 4.76ꢀ4.67 (m, 4 H), 4.51 (d, 1 H, J 8.0 Hz, b
H-1), 4.47ꢀ4.44 (m, 2 H), 4.32ꢀ3.87 (m, 38 H), 3.77 (s, 3
H, CH3O), 3.69ꢀ3.51 (m, 6 H), 2.15, 2.15, 2.13, 2.10,
ꢁ
/
45.78 (c 1.0, CHCl3); 1H NMR (400 MHz,
/
/
6.80 (dd, 4 H, Ã
/
C6H4Ã
/
), 5.76ꢀ
/
5.69 (m,
/
/
/
/
4.93 (m, 18 H), 4.81 (d, 1 H, J 8.0
MHz, D2O): d 157.41, 153.60, 120.95, 117.71 (MeOPh),
105.51 (3 b C-1), 104.06 (b C-1), 101.75 (a C-1), 101.69
(a C-1), 101.63 (a C-1), 101.63 (a C-1), 84.81, 84.57,
78.39, 78.28, 76.11, 75.86, 75.57, 74.87, 74.37, 74.16,
73.86, 73.40, 72.67, 71.97, 70.43, 63.16, 63.03, 62.88,
58.46 (some signals overlapped). Anal. Calcd for
C55H88O42: C, 46.48; H, 6.24. Found: C, 46.35; H, 6.26.
/
/
/
/
2.08, 2.05, 2.04, 2.02, 2.01, 1.98, 1.97, 2.00, 1.96, 1.93 (72
H, 24 CH3CO some signals overlapped); 13C NMR (100
MHz, CDCl3): d 170.67, 170.57, 170.49, 170.36, 170.31,

Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ
/
2056
2055
3.21. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
D
-
55.55, 20.88, 20.67, 2.59, 20.49, 20.48, 20.38 (some
signals overlapped). Anal. Calcd for C82H108O50: C,
52.01; H, 5.75. Found: C, 51.87; H, 5.74.
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (20)
/
D
-
-
-
/
3)-2,4,6-tri-O-acetyl-b-
D
/
3)-2,4,6-tri-O-acetyl-b-
D
3.23. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (22)
/
3)-2,4,6-tri-O-acetyl-a-
D
-
Deallylation of 4-methoxyphenyl 2,4,6-tri-O-acetyl-3-
O-allyl-b- -glucopyranosyl-(103)-2,4,6-tri-O-acetyl-a-
-glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b- -gluco-
pyranosyl-(103)-2,4,6-tri-O-acetyl-b- -glucopyrano-
side (450 mg, 0.342 mmol) gave acceptor 20 (350 mg,
80%): [a]D
7.358 (c 0.5, CHCl3); 1H NMR (400 MHz,
CDCl3): d 6.91ꢀ6.78 (dd, 4 H, ÃC6H4Ã), 5.22ꢀ4.96 (m,
6 H), 4.87 (dd, 1 H, J 9.6 Hz), 4.81 (d, 1 H, J 8.0 Hz, b
H-1), 4.76ꢀ4.69 (m, 2 H), 4.52 (d, 1 H, J 8.0 Hz, b H-1),
4.49 (d, 1 H, J 8.0 Hz, b H-1), 4.35ꢀ4.29 (m, 2 H), 4.18ꢀ
3.90 (m, 10 H), 3.79ꢀ3.77 (m, 4 H, CH3O), 3.70ꢀ3.55
(m, 3 H), 2.15, 2.13, 2.10, 2.09, 2.07, 2.06, 2.06, 2.04,
2.03, 2.01, 2.01, 1.99, 1.96 (12 CH3CO some signals
overlapped); 13C NMR (100 MHz, CDCl3): d 170.59,
170.45, 169.30, 169.10, 168.62 (12 CH3CO some signals
overlapped), 155.65, 150.83, 118.35, 114.43 (MeOPh),
100.68 (b C-1), 100.39 (b C-1), 100.01 (b C-1), 95.12 (a
C-1), 78.16, 75.16, 75.11, 74.09, 72.66, 72.16, 71.78,
71.70, 71.53, 71.10, 70.47, 68.67, 67.81, 67.25, 62.13,
61.76, 61.45, 61.30, 60.29, 55.54, 20.90, 20.74, 20.65,
20.57, 20.45, 20.32 (some signals overlapped). Anal.
Calcd for C55H72O34: C, 51.72; H, 5.68. Found: C,
51.66; H, 5.71.
/
3)-2,4,6-tri-O-acetyl-b-
D
-
D
/
/
3)-2,4,6-tri-O-acetyl-a-
D
-
-
-
D
/
D
/
3)-2,4,6-tri-O-acetyl-b-
D
/
D
/
3)-2,4,6-tri-O-acetyl-b-
D
ꢂ
/
/
/
/
/
Deallylation of 21 (350 mg, 0.184 mmol) gave acceptor
22 (285 mg, 84%): [a]D ꢂ
18.58 (c 1.5, CHCl3); 1H NMR
(400 MHz, CDCl3): d 6.92ꢀ6.80 (dd, 4 H, ÃC6H4Ã),
5.21ꢀ4.89 (m, 11 H), 4.82 (d, 1 H, J 8.0 Hz, b H-1),
4.79ꢀ4.69 (m, 3 H), 4.53ꢀ4.49 (m, 3 H), 4.39ꢀ3.85 (m,
29 H), 3.79ꢀ3.76 (m, 4 H, CH3O), 3.63ꢀ3.59 (m, 4 H),
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.19, 2.18, 2.15, 2.14, 2.12, 2.10, 2.09, 2.08, 2.07, 2.05,
2.04, 2.03, 2.02, 2.00, 1.99, 1.98 (18 CH3CO some signals
overlapped). Anal. Calcd for C79H104O50: C, 51.19; H,
5.66. Found: C, 51.30; H, 5.61.
3.24. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (23)
/
3)-2,4,6-tri-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
D-
/
D
-
/
D-
/
3)-2,4,6-tri-O-acetyl-b-
D
-
/
3)-2,4,6-tri-O-acetyl-a-
D
-
-
-
/
3)-2,4,6-tri-O-acetyl-b-
D
3.22. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-3-O-allyl-b-
D-
/
3)-2,4,6-tri-O-acetyl-b-
D
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (21)
/
3)-2,4,6-tri-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-2,4,6-tri-O-acetyl-a-
D
-
/
D-
/
D
-
-
-
Donor 12 (145 mg, 0.14 mmol) was coupled with
acceptor 22 (260 mg, 0.14 mmol) to give 23 (240 mg,
/
3)-2,4,6-tri-O-acetyl-b-
D
/
3)-2,4,6-tri-O-acetyl-b-
D
63%): [a]D
CDCl3): d 8.05ꢀ
4 H, ÃC6H4Ã), 5.86 (dd, 1 H, J 9.6 Hz), 5.69 (dd, 1 H, J
9.6 Hz), 5.35 (dd, 1 H, J 9.6 Hz), 5.21ꢀ4.87 (m, 12 H),
4.80 (d, 2 H, J 8.0 Hz, 2b H-1), 4.71ꢀ4.67 (m, 3 H),
4.51ꢀ4.41 (m, 4 H), 4.31ꢀ3.87 (m, 25 H), 3.79ꢀ3.69 (m,
5 H, CH3O), 3.67ꢀ3.50 (m, 3 H), 2.14, 2.13, 2.12, 2.09,
ꢂ
/
17.98 (c 1.0, CHCl3); 1H NMR (400 MHz,
/
7.25 (m, 20 H, 4 PhCO), 6.90ꢀ6.77 (dd,
/
/
/
Donor 8 (200 mg, 0.258 mmol) was coupled with
acceptor 20 (330 mg, 0.258 mmol) to give 21 (387 mg,
/
/
79%): [a]D
CDCl3): d 6.93ꢀ
1 H, ÃCH ꢀ), 5.21ꢀ
Hz, b H-1), 4.73ꢀ4.68 (m, 2 H), 4.51ꢀ
4.37ꢀ3.85 (m, 21 H), 3.79ꢀ3.77 (m, 4 H, CH3O), 3.61ꢀ
ꢂ
/
5.238 (c 1.0, CHCl3); 1H NMR (400 MHz,
/
/
/
/
6.79 (dd, 4 H, Ã
4.83 (m, 15 H), 4.82 (d, 1 H, J 8.0
4.47 (m, 2 H),
/
C6H4Ã
/
), 5.76ꢀ
/
5.69 (m,
/
/
/
/
2.08, 2.07, 2.06, 2.05, 2.04, 2.03, 2.01, 1.98, 1.96, 1.93,
1.88, 1.85 (63 H, 21 CH3CO some signals overlapped);
13C NMR (100 MHz, CDCl3): d 170.51, 170.47, 170.43,
170.40, 170.26, 169.99, 169.37, 169.25, 169.06, 168.93,
168.82, 168.67, 168.47 (21 CH3CO some signals over-
lapped), 165.96, 165.79, 164.9 (4 PhCO some signals
overlapped), 155.54, 150.87, 118.47, 114.47 (MeOPh),
101.09 (b C-1), 100.44 (4 b C-1), 95.33 (a C-1), 95.23 (a
C-1), 95.03 (a C-1), 76.33, 75.39, 5.07, 74.93, 74.82,
74.45, 73.08, 72.72, 72.34, 71.92, 71.88, 71.61, 71.55,
71.48, 71.30, 70.37, 70.29, 69.71, 69.16, 68.42, 67.91,
67.86, 67.40, 67.32, 62.55, 61.75, 61.39, 55.53, 21.04,
20.84, 20.79, 20.70, 20.65, 20.57, 20.52, 20.46, 20.39,
20.35 (some signals overlapped). Anal. Calcd for
/
/
/
/
/
3.49 (m, 4 H), 2.19, 2.18, 2.16, 2.14, 2.12, 2.10, 2.09,
2.08, 2.07, 2.05, 2.04, 2.03, 2.02, 1.98, 1.97, 1.96 (18
CH3CO some signals overlapped); 13C NMR (100 MHz,
CDCl3): d 170.67, 170.57, 170.39, 170.35, 169.33,
169.18, 169.13, 168.84, 168.62 (18 CH3CO some signals
overlapped), 155.64, 150.83, 134.02, 118.35, 116.84,
114.42 (CH2ꢀ
/
CHÃ
/
CH2Ã, MeOPh), 100.77 (b C-1),
/
100.65 (b C-1), 100.48 (b C-1), 100.02 (b C-1), 95.12 (a
C-1), 94.90 (a C-1), 79.90, 78.17, 75.33, 74.95, 74.61,
72.26, 72.00, 71.88, 71.68, 71.52, 71.07, 70.43, 69.05,
68.08, 67.82, 67.77, 67.36, 67.26, 62.10, 61.88, 61.38,

2056
Y. Zeng, F. Kong / Carbohydrate Research 338 (2003) 2047ꢀ2056
/
C125H146O67: C, 55.19; H, 5.41. Found: C, 55.10; H,
5.37.
References
1. Sasaki, T.; Takasuka, N. Carbohydr. Res. 1976, 47, 99ꢀ
105.
/
2. (a) Molinaro, A.; Lanzetta, R.; Mancino, A.; Evidente, A.;
3.25. 4-Methoxyphenyl b-
D
-glucopyranosyl-(10
/
3)-a-D-
Rosa, M. D.; Ianaro, A. Carbohydr. Res. 2000, 329, 441ꢀ
/
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (24)
/
3)-b-
3)-b-
3)-b-
D
D
D
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranosyl-(10
/
3)-a-
D-
445;
(b) Bao, X.; Liu, C.; Fang, J.; Li, X. Carbohydr. Res. 2001,
/
/3)-a-
D-
/
/3)-b-D-
336, 127ꢀ
3. (a) Sharp, J. K.; Valent, B.; Albersheim, P. J. Biol. Chem.
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(b) Ning, J.; Zhang, W.; Yi, Y.; Yang, G.; Wu, Z.; Yi, J.;
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hydr. Res. 1993, 245, 81ꢀ96;
(b) Katsuraya, K.; Shoji, T.; Inazawa, K.; Nakashima, H.;
Yamamoto, N.; Uryu, T. Macromolecules 1994, 27, 6695ꢀ
/
133.
/
Compound 24 (120 mg) was obtained by deacylation of
1
/
23 (240 mg, 0.088 mmol): [a]D
NMR (400 MHz, D2O): d 7.06ꢀ
5.30 (s, 3 H, 3 a H-1), 4.98 (d, 1 H, J 7.6 Hz, b H-1),
4.76ꢀ4.69 (m, 4 H, 4 b H-1), 4.03ꢀ
3.29 (m, 45 H); 13C
ꢂ
/
8.38(c 1.5, H2O); H
/
6.89 (dd, 4 H,ÃC6H4Ã),
/
/
/
/
/
/
NMR (100 MHz, D2O): d 157.56, 153.64, 121.14, 117.98
(MeOPh), 105.58 (4 b C-1), 103.74 (b C-1), 101.77 (3 a
C-1), 87.16, 85.02, 78.72, 78.38, 76.28, 75.51, 75.04,
74.38, 74.01, 72.78, 72.41, 70.83, 70.69, 63.54, 63.40,
63.19, 58.83 (some signals overlapped). Anal. Calcd for
C55H88O42: C, 46.48; H, 6.24. Found: C, 46.60; H, 6.22.
6699;
(c) Katsuraya, K.; Ikusima, N.; Takahashi, N.; Shoji, T.;
Nakashima, H.; Yamamoto, N.; Yoshida, T.; Uryu, T.
Carbohydr. Res. 1994, 260, 51ꢀ
/61.
5. (a) Good, F.; Schuerch, C. Macromolecules 1985, 18, 595ꢀ
/
598;
(b) Zhang, P.; Cheung, P. C. K. Biosci. Biotechnol.
Biochem. 2002, 66, 1052ꢀ
6. (a) Zeng, Y.; Ning, J.; Kong, F. Tetrahedron Lett. 2002, 43,
3279ꢀ3233.;
(b) Zeng, Y.; Ning, J.; Kong, F. Carbohydr. Res. 2003, 338,
307ꢀ311.
7. Ogawa, T.; Yamamoto, H. Carbohydr. Res. 1985, 137, 79ꢀ
/
1056.
/
Acknowledgements
/
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).
/
88.
8. Schmidt, R. R.; Kinzy, W. Adv. Carbohydr. Chem. Bio-
chem. 1994, 50, 21ꢀ125.
/