Synthesis of β-(1→6)-branched (1→3)-glucododecaose and -glucopentadecaose with alternate β- and α-bonds in the backbone

Article abstract of DOI:10.1016/S0008-6215(03)00354-9

β-D-Glcp-(1→3)-[β-D-Glcp-(1→6)]-α-D-Glcp- (1→3)-{β-D-Glcp-(1→3)-[β-D-Glcp-(1→6)] -α-D-Glcp-(1→3)}_2-3-β-D-Glcp-(1→3)-[β-D- Glcp-(1→6)]-β-D-Glcp were synthesized as their methoxyphenyl glycosides in a concise way with a trisaccharide as the building block.

Full text of DOI:10.1016/S0008-6215(03)00354-9

Carbohydrate Research 338 (2003) 2203Á2212
/
www.elsevier.com/locate/carres
Synthesis of b-(10
/
6)-branched (10
/
3)-glucododecaose and
-glucopentadecaose with alternate b- and a-bonds in the backbone
Zicheng Wu, Jun Ning, Fanzuo Kong*
Research Center for Eco-Environmental Sciences, Academia Sinica, P.O. Box 2871, Beijing 100085, PR China
Received 29 May 2003; accepted 12 July 2003
Abstract
b-
(10
building block.
D
-Glcp-(10
/
3)-[b-
D
-Glcp-(10
/
6)]-a-
D
-Glcp-(10
/
3)-{b-
D
-Glcp-(10
/
3)-[b-
D
-Glcp-(10
/
6)]-a-
D
-Glcp-(10
/
3)}2Á3-b-D-Glcp-
/
3)-[b- -Glcp-(10
D
/
6)]-b- -Glcp were synthesized as their methoxyphenyl glycosides in a concise way with a trisaccharide as the
D
# 2003 Elsevier Ltd. All rights reserved.
Keywords: Oligosaccharide; Synthesis; Glucose
1. Introduction
and a glucopentadecaose containing five trisaccharide
units.
In continuation of our research on developing new
immunopotentiating reagents, we have synthesized the
heptasaccharide1 repeating unit of lentinan and its
anologues,2 and the pentasaccharide fragments3 of
Epicoccum nigrum Ehrenb. ex Schlecht. It was interest-
ing to find that not only the heptasaccharide shows
strong antitumor activity as we expected. But also a
2. Results and discussion
As shown in Scheme 1, coupling5 of the trisaccharide
donor 12 with the trisaccharide acceptor 2, which was
obtained by condensation of 1 with 4-methoxyphenol,
followed by deallylation, afforded the hexasaccharide 3
with an a-linkage6 between the two trisaccharide
moieties (68.2%), the same as that reported for the
coupling of two trisaccharides with similar structures.2
glucohexaose, b-
Glcp-(103)-b-
D
-Glcp-(10
/
3)-[b-
D
-Glcp-(10
-Glcp-(10
/
6)]-a-
D
-
/
D
-Glcp-(10
/
3)-[b-
D
/
6)]-D
-
Glcp, has good immunoregulating activity.2 Bioassays
showed that in combination with the chemotherapeutic
agent, cyclophosphamide (CPA), the glucohexaose at a
7
Deallylation of 3 with PdCl2 in MeOH smoothly gave
dose of 0.5Á1 mg/kg substantially increased the inhibi-
/
the hexasaccharide acceptor 4 (85.2%). Condensation of
1 with 4 furnished the nonasaccharide 5 (60.7%), and
subsequent deallylation gave the nonasaccharide accep-
tor 6 (81.1%). Coupling of 78 with 6 yielded the
dodecasaccharide 8 (54.2%), and subsequent deacylation
tion of S180 for CPA, but decreased the toxicity caused
by CPA. It was noted that this hexasaccharide was not
fully b-linked like the repeating unit of lentinan4 but
contained one a-linkage between the two trisaccharide
moieties. For a detailed study on the mechanism of
action of the glucose hexasaccharide, a variety of model
compounds was needed. We present herein the syntheses
of a glucododecaose consisting four trisaccharide units
gave the target dodecaoside 9 (86.3%). The H and 13C
1
NMR spectra of 9 showed all of the characteristic
signals such as d 5.19 with J1,2 3.2 Hz for 3 a-H-1, d
4.68Á4.10 with J1,2 8.0 Hz for 9 b-H-1, d 103.5, 101.9,
/
and 101.8 for 3 a-C-1, and d 105.5 and 105.2 for 9 b-C-
1. The pentadecasaccharide 13 was obtained by the same
reaction sequence, i.e., condensation of 1 with 6 gave 10
(48.1%), deallylation of 10 afforded 11 (80.3%), subse-
quent condensation of 11 with 7 furnished 12 (42.7%),
* 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/S0008-6215(03)00354-9

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Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á2212
/
Scheme 1. Reagents and conditions: (a) TMSOTf, CH2Cl2, ꢁ
/
20 8C to rt, 3Á
/
5 h; (b) PdCl2 in CH2Cl2ÁCH3OH, rt, 3 h; (c) satd
/
NH3ÁMeOH, rt, 7 d.
/
and finally deprotection (85.8%) yielded the target
1
105.4 and 105.2 for 11 b-C-1. Bioactivity testing of 9 and
13 is in progress, and the results will be reported in due
course.
pentadecasaccharide. The H and 13C NMR spectra of
13 showed characteristic signals such as d 5.29 with J1,2
3.2 Hz for 4 a-H-1, d 5.04Á
/
4.10 with J1,2 7.8 Hz for 11
In the synthesis of the dodecasaccharide 8, another
strategy with coupling of two hexasaccharides was also
b-H-1, d 103.4, 101.8, and 101.7 for 4 a-C-1, and d

Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á
/2212
2205
tried. Thus, the coupling of 7 with 2 gave the hexasac-
charide 14, and subsequent oxidative cleavage of the
methoxyphenyl group with CAN, followed by trichloro-
acetimidation, gave the hexasaccharide donor 15
(72.5%) (Scheme 2). Coupling of 4 with 15 was carried
out as a parallel experiment with the condensation of 1
and 6, but no expected coupling product was obtained
except the decomposed byproduct of the donor. This
indicated that the hexasaccharide donor and the hex-
asaccharide acceptor may be not matched, while the
trisaccharide donor and the hexa-, nano-, or dodeca-
saccharide acceptor were matched.
Analytical LC was performed with a Gilson HPLC
consisting of a pump (model 306), stainless steel column
packed with silica gel (Spherisorb SiO2, 10ꢂ
4.6ꢂ250 mm), differential refractometer (132-RI De-
tector), UV/vis detector (model 118). EtOAcÁpetroleum
ether (bp 60Á90 8C) was used as the eluent at a flow rate
of 1Á4 mL/min. Solutions were concentrated at a
temperature B60 8C under diminished pressure.
/300 or
/
/
/
/
/
3.2. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (2)
D-
/
D-
/
D-
In summary, an efficient method for the construction
3)-linked glucododecaose
of b-(10
/
6)-branched (10
/
and glucopentadecaose with alternate b- and a-linkages
in the backbone was achieved using trisaccharide as the
building block. This method should be suitable for
synthesis of high oligosaccharides of similar structure.
Compound 1 (10 g, 8.38 mmol) and 4-methoxyphenol
(1.0 g, 0.926 mmol) were dried together under high
vacuum for 2 h, then dissolved in anhyd CH2Cl2 (150
mL). TMSOTf (100 mL, 0.870 mmol) was added
dropwise at ꢁ20 8C with nitrogen protection. The
/
reaction mixture was stirred for 3 h, during which time
the temperature was gradually raised to ambient tem-
perature. Then the mixture was neutralized with Et3N.
Concentration of the reaction mixture, followed by
purification on a silica gel column with 2:1 petroleum
3. Experimental
3.1. General methods
etherÁ
tri-O -acetyl-3-O -allyl-b-
[2,3,4,6-tetra-O-benzoyl-b-
2,4-di-O-acetyl-b- -glucopyranoside (8.38 g, 78.4%) as
a foamy solid: [a]D
(CDCl3, 400 MHz): d 8.04Á
6.92Á6.83 (dd, 4 H, MPC6H4ꢀ
J4,5 9.7 Hz, H-4), 5.76Á5.68 (m, 1 H, CH2 ꢁ
CH2O), 5.64 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.49
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.18 (m, 1 H, CH2ꢁ
CHCH2O), 5.14Á5.04 (m, 2 H), 5.00 (dd, 1 H, J3,4
J4,5 9.7 Hz, H-4), 4.99 (d, 1 H, J1,2 7.9 Hz, H-1), 4.88
/
EtOAc as the eluent gave 4-methoxyphenyl 2,4,6-
-glucopyranosyl-(1 03)-
-glucopyranosyl-(106)]-
Melting points were determined with a ‘Mel-Temp’
apparatus. Optical rotations were determined with a
D
/
D
/
PerkinÁElmer model 241-MC automatic polarimeter for
/
D
solutions in a 1-dm, jacketed cell. 1H, 13C, and 2D NMR
spectra were recorded with Varian XL-400 spectro-
meters for solutions in CDCl3 or in D2O as indicated.
Chemical shifts are expressed in d-units (ppm) down-
field from the Me4Si absorption. Mass spectra were
recorded with a VG PLATFORM mass spectrometer
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
1
ꢀ
/
23.88 (c 1.0, CHCl3); H NMR
7.27 (m, 20 H, 4 BzꢀH),
), 5.82 (dd, 1 H, J3,4
CH ꢀ
/
/
/
/
ꢃ
/
ꢃ
/
/
/
/
ꢃ
/
ꢃ
/
/
/
ꢃ
/
ꢃ
/
(dd, 1 H, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 4.75 (d, 1 H, J1,2
7.9 Hz, H-1), 4.74 (m, 1 H), 4.61 (dd, J5,6 2.7 Hz, J6,6
by elution of a column (8ꢂ
300 mm, 35ꢂ400 mm) of silica gel (100Á
EtOAcÁpetroleum ether (bp 60Á90 8C) as the eluent.
/
100 mm, 16ꢂ
/
240 mm, 18ꢂ
/
12.1 Hz, H-6), 4.49 (d, 1 H, J1,2 7.9 Hz, H-1), 4.47Á
(m, 1 H), 4.28 (dd, J5,6 4.7 Hz, J6,6 12.1 Hz, H-6), 4.04Á
4.00 (m, 4 H), 3.90Á3.75 (m, 7 H), 3.57Á3.53 (m, 2 H),
/
4.45
/
/200 mesh) with
/
/
/
/
/
2.15, 2.10, 2.08, 2.06, 1.90 (s, 15 H, 5 CH3 CO); 13C
NMR (CDCl3, 100 MHz): d 170.5, 169.4, 169.1, 168.6,
166.0, (5 C, 5 CH3CO), 165.6, 165.1, 155.6, 150.9 (4 C, 4
COPh), 101.0, 100.4, 99.8 (C-1IÁIII), 79.7, 78.2, 74.4,
72.9, 72.7, 72.3, 72.2, 71.9, 69.4, 69.1, 68.6, 67.9, 62.9,
62.0, 55.6 (C-2, 3, 4, 5, 6IÁIII), 20.8, 20.7, 20.6, 20.3.
Anal. Calcd for C66H68O26: C, 62.07; H, 5.33. Found: C,
62.25; H, 5.24.
The resultant trisaccharide was dissolved in MeOH
(100 mL), and then PdCl2 (350 mg) was added. After
stirring for 3 h at room temperature (rt), TLC (1.5:1
petroleum etherÁEtOAc) indicated that the reaction was
/
complete. The mixture was filtered, the solution was
concentrated to dryness, and the resultant residue was
purified by flash chromatography (1.5:1 petroleum
Scheme 2. Reagents and conditions: (a) TMSOTf, CH2Cl2,
20 8C to rt, 3Á5 h; (b) i. CAN in MeCNÁH2O, rt, 3 h; ii.
CH2Cl2, CCl3CN, K2CO3, rt, 10 h.
ꢁ
/
/
/

2206
Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á2212
/
etherÁ
[a]D
MHz): d 8.04Á
H, MPC6H4ꢀ), 5.81 (dd, 1 H, J3,4
5.64 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.48 (dd, J1,2 7.9
/
EtOAc) to give 2 (7.04 g, 86.7%) as a foamy solid:
20.48 (c 1.0, CHCl3); 1H NMR (CDCl3, 400
7.28 (m, 20 H, 4 BzꢀH), 6.90Á6.85(dd, 4
J4,5 9.7 Hz, H-4),
(CDCl3, 100 MHz): d 170.6, 170.5, 170.4, 169.5, 169.4,
169.3, 169.3, 169.2, 168.8, 168.6 (10 C, 10 COCH3),
166.0, 166.0, 165.6, 165.6, 165.4, 165.1, 165.1, 165.1 (8
C, 8 COPh), 101.5, 100.8, 100.6, 100.4, 99.8 (5 b-C-1),
93.3 (a-C-1), 79.9, 78.1, 74.9, 74.4, 72.9, 72.6, 72.5, 72.4,
72.3, 72.2, 72.1, 72.0, 71.9, 71.0, 69.7, 69.5, 69.1, 68.6,
68.4, 67.8, 67.6, 62.9, 62.4, 62.0, 61.3, 60.3, 55.6 (C-2, 3,
4, 5, 6IÁVI), 21.2, 20.7, 20.6, 20.5, 20.5, 20.4, 20.4. Anal.
Calcd for C122H124O50: C, 61.31; H, 5.19. Found: C,
61.59; H, 5.02.
ꢀ
/
/
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
Hz, J2,3 9.7 Hz, H-2), 5.12 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz,
H-2), 4.99 (d, 1 H, J1,2 7.9 Hz, H-1), 4.91 (m, 1 H), 4.75
(d, 1 H, J1,2 7.9 Hz, H-1), 4.72Á
J5,6 2.7 Hz, J6,6 12.1 Hz, H-6), 4.50 (d, 1 H, J1,2 7.9 Hz,
H-1), 4.47Á4.42 (m, 1 H), 4.28 (dd, J5,6 4.7 Hz, J6,6 12.1
Hz, H-6), 4.04Á3.99 (m, 2 H), 3.89Á3.77 (m, 7 H), 3.62Á
/4.65 (m, 3 H), 4.61 (dd,
/
/
/
/
3.58 (m, 2 H), 2.17, 2.12, 2.08, 2.05, 1.97 (s, 15 H, 5
CH3CO); 13C NMR (CDCl3, 100 MHz): d 171.1, 170.4,
169.4, 168.5, 166.0 (5 C, 5 CH3CO), 165.6, 165.1, 155.6,
150.9 (4 C, 4 COPh), 100.8, 100.4, 99.8 (C-1IÁIII), 78.7,
74.3, 74.0, 73.8, 72.9, 72.6, 72.2, 71.8, 71.6, 70.4, 69.4,
68.5, 67.8, 62.9, 61.8, 55.6 (C-2, 3, 4, 5, 6IÁIII), 20.8, 20.7,
20.5, 20.3. Anal. Calcd for C63H64O26: C, 61.17; H, 5.18.
Found: C, 61.46; H, 5.26.
3.4. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (4)
D-
/
D
-
-
/
D-
/
D-
/
D
/
D-
3.3. 4-Methoxyphenyl 3-O-allyl-2,4,6-tri-O-acetyl-b-
D
-
To a solution of 3 (8.7 g, 3.64 mmol) in MeOH (100 mL)
was added PdCl2 (250 mg). After stirring the mixture for
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (3)
/
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-b-
D
-
/
D
-
3 h at rt, TLC (1:1 petroleum etherÁEtOAc) indicated
/
/
D
-
that the reaction was complete. The mixture was filtered,
the solution was concentrated to dryness, and the
resultant residue was purified by flash chromatography
/
D-
/
D-
(1:1 petroleum etherÁ
a foamy solid: [a]D
(CDCl3, 400 MHz): d 8.03Á
6.94Á6.90 (dd, 4 H, MPC6H4ꢀ
J4,5 9.7 Hz, H-4), 5.82 (dd, 1 H, J3,4
H-4), 5.65 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.62 (dd, 1
H, J2,3 J3,4 9.7 Hz, H-3), 5.49 (dd, J1,2 7.9 Hz, J2,3
/
EtOAc) to give 4 (7.28 g, 85.2%) as
1
ꢀ
/
24.58 (c 1.0, CHCl3); H NMR
7.24 (m, 40 H, 8 BzꢀH),
), 5.88 (dd, 1 H, J3,4
J4,5 9.7 Hz,
Compound 1 (7.9 g, 6.62 mmol) and 2 (6.8 g, 5.50 mmol)
were dried together under high vacuum for 2 h, then
dissolved in anhyd CH2Cl2 (200 mL). TMSOTf (100 mL,
/
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
0.87 mmol) was added dropwise at ꢁ
/
20 8C with
ꢃ
/
ꢃ
/
nitrogen 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
ꢃ
/
ꢃ
/
9.7 Hz, H-2), 5.39 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.16
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.02 (d, 1 H, J1,2 7.9
Hz, H-1), 4.99 (dd, 1 H, J3,4
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 4.85 (d, 1 H, J1,2 3.6
Hz, H-1), 4.78 (d, 1 H, J1,2 7.9 Hz, H-1), 4.77Á4.72 (m, 4
H), 4.68Á4.63 (m, 5 H), 4.61 (d, 1 H, J1,2 7.9 Hz, H-1),
4.48 (d, 1 H, J1,2 7.9 Hz, H-1), 4.48Á4.42 (m, 3 H), 4.30
(dd, 1 H, J5,6 5.1 Hz, J6,6 12.4 Hz, H-6), 4.19 (dd, 1 H,
J5,6 4.2 Hz, J6,6 12.4 Hz, H-6), 4.14Á4.09 (m, 3 H), 4.01Á
3.98 (m, 2 H), 3.92Á3.83 (m, 7 H), 3.80 (s, 3 H, CH3O),
3.78Á3.74 (m, 1 H), 3.61Á3.57 (m, 3 H), 3.47Á3.42 (m, 1
ꢃ
/
J4,5
ꢃ/9.7 Hz, H-4), 4.89
gel column with 1.5:1 petroleum etherÁ
eluent gave the hexasaccharide 3 (8.96 g, 68.2%) as a
foamy solid: [a]D
16.38 (c 1.0, CHCl3); 1H NMR
(CDCl3, 400 MHz): d 8.16Á7.21 (m, 40 H, 8 BzꢀH),
6.96Á6.82 (dd, 4 H, MPC6H4ꢀ), 5.89 (dd, 1 H, J3,4
J4,5 9.7 Hz, H-4), 5.83 (dd, 1 H, J3,4 J4,5 9.7 Hz,
H-4), 5.80Á5.68 (m, 1 H, CH2ꢁCH ꢀCH2O), 5.65 (dd, 1
H, J2,3 J3,4 9.7 Hz, H-3), 5.61 (dd, 1 H, J2,3 J3,4
9.7 Hz, H-3), 5.50 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2),
5.55Á5.49 (m, 5 H), 5.49 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-
2), 5.19Á5.12 (m, 3 H), 5.03 (d, 1 H, J1,2 7.9 Hz, H-1),
5.01Á4.95 (m, 2 H), 4.90 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-
2), 4.86 (d, 1 H, J1,2 3.6 Hz, H-1), 4.83Á4.72 (m, 4 H),
4.62 (d, 1 H, J1,2 7.9 Hz, H-1), 4.61Á4.56 (m, 3 H), 4.48
(d, 1 H, J1,2 7.9 Hz, H-1), 4.46Á4.39 (m, 3 H), 4.23Á4.11
(m, 5 H), 4.30Á4.3.98 (m, 4 H), 3.90Á3.81 (m, 6 H), 3.80
(s, 3 H, CH3O), 3.77Á3.72 (m, 1 H), 3.62Á3.52 (m, 2 H),
3.50Á3.42 (m, 2 H), 2.43, 2.11, 2.10, 2.09, 2.07, 2.04,
1.99, 1.98, 1.97, 1.95 (s, 30 H, 10 CH3CO); 13C NMR
/EtOAc as the
/
/
ꢀ
/
/
/
/
/
/
ꢃ
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
/
/
/
/
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
H), 2.41, 2.11, 2.10, 2.09, 2.08, 2.06, 2.00, 1.99, 1.98, 1.98
(s, 30 H, 10 CH3CO); 13C NMR (CDCl3, 100 MHz): d
170.5, 170.5, 170.4, 170.4, 169.6, 169.4, 169.3, 169.3,
169.2, 168.8 (10 C, 10 COCH3), 166.0, 166.0, 165.6,
165.6, 165.5, 165.1, 165.1, 165.1 (8 C, 8 COPh), 101.5,
100.6, 100.4, 100.4, 99.8 (5 b-C-1), 93.4 (a-C-1), 78.1,
75.1, 74.4, 74.4, 74.0, 72.9, 72.6, 72.5, 72.4, 72.3, 72.2,
72.1, 71.9, 71.8, 71.6, 71.1, 70.6, 70.6, 69.6, 69.5, 69.1,
68.6, 68.3, 67.8, 67.7, 62.9, 62.4, 61.9, 61.4, 55.9 (C-2, 3,
4, 5, 6IÁVI), 21.2, 20.9, 20.7, 20.6, 20.5, 20.5, 20.4, 20.4.
Anal. Calcd for C119H120O50: C, 60.82; H, 5.11. Found:
C, 60.53; H, 5.01.
/
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Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á
/2212
2207
3.5. 4-Methoxyphenyl 3-O-allyl-2,4,6-tri-O-acetyl-b-
D
-
20.6, 20.4, 20.2. Anal. Calcd for C178H180O74: C, 61.03;
H, 5.14. Found: C, 61.31; H, 5.03.
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (5)
/
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-b-
D-
D-
D-
/
D-
/
D-
3.6. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (6)
D-
/
/
D-
D-
D
-
/
D-
/
D-
/
D-
/
D-
/
/
/
D-
/
D-
/
D-
/
Compound 1 (4.3 g, 3.60 mmol) and 4 (7.0 g, 2.98 mmol)
were dried together under high vacuum for 2 h, then
dissolved in anhyd CH2Cl2 (150 mL). TMSOTf (150 mL,
/
D-
1.31 mmol) was added dropwise at ꢁ20 8C with
/
To a solution of 5 (6 g, 1.71 mmol) in MeOH (100 mL)
was added PdCl2 (200 mg). After stirring the mixture for
nitrogen 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
3 h at rt, TLC (2:1 petroleum etherÁEtOAc) indicated
/
that the reaction was complete. The mixture was filtered,
the solution was concentrated to dryness, and the
resultant residue was purified by flash chromatography
gel column with 1:1.5 petroleum etherÁ
eluent gave the product 5 (6.33 g, 60.7%) as a syrup: [a]D
23.58 (c 1.0, CHCl3); 1H NMR (CDCl3, 400 MHz): d
8.02Á7.26 (m, 60 H, 12 BzꢀH), 6.95Á6.84 (dd, 4 H,
MPC6H4ꢀ), 5.90 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4),
5.89 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.82 (dd, 1 H,
J3,4 J4,5 9.7 Hz, H-4), 5.80Á5.68 (m, 1 H, CH2ꢁ
CH ꢀCH2O), 5.64 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.61 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.59 (dd, 1 H,
J2,3 J3,4 9.7 Hz, H-3), 5.50 (dd, J1,2 7.9 Hz, J2,3 9.7
Hz, H-2), 5.45 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.40
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.22Á5.14 (m, 2 H),
5.12Á5.06 (m, 1 H, CH2ꢁCH ꢀCH2O), 5.01 (d, 1 H, J1,2
7.9 Hz, H-1), 5.00 (d, 1 H, J1,2 7.9 Hz, H-1), 4.98 (dd,
J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 4.96 (dd, 1 H, J3,4 J4,5
9.7 Hz, H-4), 4.95 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4),
4.84 (d, 1 H, J1,2 3.6 Hz, H-1), 4.80 (d, 1 H, J1,2 3.6 Hz,
H-1), 4.78 (d, 1 H, J1,2 7.9 Hz, H-1), 4.76Á4.72 (m, 4 H),
4.70Á
4.59 (m, 5 H), 4.58 (d, 1 H, J1,2 7.9 Hz, H-1), 4.52Á
/EtOAc as the
(2:1 petroleum etherÁ
a foamy solid: [a]D
(CDCl3, 400 MHz): d 8.02Á
6.96Á6.84 (dd, 4 H, MPC6H4ꢀ
J4,5 9.7 Hz, H-4), 5.89 (dd, 1 H, J3,4
H-4), 5.82 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.67 (dd, 1
H, J2,3 J3,4 9.7 Hz, H-3), 5.62 (dd, 1 H, J2,3 J3,4
9.7 Hz, H-3), 5.59 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
/
EtOAc) to give 6 (4.80 g, 81.1%) as
1
ꢀ
/
30.68 (c 1.0, CHCl3); H NMR
7.26 (m, 60 H, 12 BzꢀH),
), 5.91 (dd, 1 H, J3,4
J4,5 9.7 Hz,
ꢀ
/
/
/
/
/
/
/
/
ꢃ
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
5.49 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.41 (dd, J1,2 7.9
Hz, J2,3 9.7 Hz, H-2), 5.39 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz,
H-2), 5.19 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.03 (d, 1
H, J1,2 7.9 Hz, H-1), 5.01 (d, 1 H, J1,2 7.9 Hz, H-1), 4.98
ꢃ
/
ꢃ
/
/
/
/
/
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 4.96 (dd, 1 H, J3,4
J4,5 9.7 Hz, H-4), 4.94 (dd, 1 H, J3,4 J4,5 9.7 Hz,
H-4), 4.84 (d, 1 H, J1,2 3.6 Hz, H-1), 4.81 (d, 1 H, J1,2 3.6
Hz, H-1), 4.79 (d, 1 H, J1,2 7.9 Hz, H-1), 4.77Á4.72 (m, 6
H), 4.68Á4.62 (m, 2 H), 4.62 (d, 1 H, J1,2 7.9 Hz, H-1),
4.59 (d, 1 H, J1,2 7.9 Hz, H-1), 4.58Á4.53 (m, 4 H), 4.52Á
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
/
/
/
/
/
4.68 (m, 2 H), 4.64 (d, 1 H, J1,2 7.9 Hz, H-1), 4.63Á
/
4.45 (m, 3 H), 4.44 (d, 1 H, J1,2 7.9 Hz, H-1), 4.27 (dd, 1
H, J5,6 4.7 Hz, J6,6 12.4 Hz, H-6), 4.17 (dd, 1 H, J5,6 5.1
/
4.45
(m, 3 H), 4.44 (d, 1 H, J1,2 7.9 Hz, H-1), 4.20 (dd, 1 H,
J5,6 4.7 Hz, J6,6 12.4 Hz, H-6), 4.18 (dd, 1 H, J5,6 5.1 Hz,
Hz, J6,6 12.4 Hz, H-6), 4.15Á
(m, 12 H), 3.81 (s, 3 H, CH3O), 3.80Á
3.62Á3.55 (m, 3 H), 3.47Á3.42 (m, 3 H), 2.43, 2.31, 2.11,
/
4.08 (m, 5 H), 4.05Á
/
3.84
/
3.74 (m, 2 H),
J6,6 12.4 Hz, H-6), 4.15Á
H), 3.81(s, 3 H, CH3O), 3.80Á
H, H-5), 3.54 (m, 1 H, H-5), 3.49Á
/
4.08 (m, 3 H), 4.04Á
3.74 (m, 2 H), 3.62 (m, 1
3.41 (m, 3 H), 2.43,
/
3.82 (m, 14
/
/
/
2.09, 2.09, 2.08, 2.08, 2.03, 2.00, 2.00, 1.99, 1.99, 1.95,
1.94, 1.88 (s, 45 H, 15 CH3CO); 13C NMR (CDCl3, 100
MHz): d 170.8, 170.7, 170.6, 170.6, 170.4, 170.4, 170.3,
169.7, 169.5, 169.4, 169.3, 169.3, 169.2, 169.0, 168.8 (15
C, 15 COCH3), 166.0, 166.0, 166.0, 165.9, 165.6, 165.6,
165.5, 165.1, 165.1, 165.1, 165.1 (12 C, 12 COPh), 101.6,
101.4, 100.7, 100.4, 100.3, 100.1, 99.8 (7 b-C-1), 93.9,
93.5 (2 a-C-1), 78.1, 75.1, 74.9, 74.4, 74.1, 74.1, 73.6,
72.9, 72.6, 72.2, 72.4, 72.2, 72.2, 72.1, 72.0, 71.9, 71.6,
71.6, 70.8, 70.5, 69.8, 69.7, 69.5, 69.2, 69.1, 69.0, 68.6,
68.3, 67.9, 67.6, 62.9, 62.8, 62.4, 62.0, 61.8, 61.5, 61.3,
55.6 (C-2, 3, 4, 5, 6), 21.3, 21.2, 20.8, 20.7, 20.6, 20.4,
20.3. Anal. Calcd for C175H176O74: C, 60.69; H, 5.09.
Found: C, 61.01; H, 5.16.
/
2.32, 2.12, 2.11, 2.09, 2.08, 2.08, 2.06, 2.00, 2.00, 1.99,
1.95, 1.95, 1.93, 1.88 (s, 45 H, 15 CH3CO); 13C NMR
(CDCl3, 100 MHz): d 170.8, 170.6, 170.5, 170.4, 170.4,
169.8, 169.5, 169.5, 169.4, 169.3, 169.2, 169.2, 168.9,
168.8, 168.6 (15 C, 15 COCH3), 166.0, 166.0, 166.0,
165.6, 165.6, 165.6, 165.5, 165.1, 165.1, 165.1, 165.1 (12
C, 12 COPh), 101.6, 101.5, 100.6, 100.6, 100.4, 100.1,
99.8 (7 b-C-1), 93.8, 93.5 (2 a-C-1), 80.0, 78.1, 75.5, 74.9,
74.4, 74.1, 73.6, 72.9, 72.6, 72.5, 72.4, 72.2, 72.2, 72.1,
72.0, 71.9, 71.6, 71.6, 70.8, 70.5, 69.8, 69.7, 69.5, 69.2,
69.1, 69.0, 68.6, 68.3, 67.9, 67.6, 62.9, 62.8, 62.4, 62.0,
61.5, 61.3, 60.3, 55.6 (C-2, 3, 4, 5, 6), 21.2, 20.8, 20.7,

2208
Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á2212
/
3.7. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (8)
D
-
71.6, 71.1, 70.6, 70.5, 69.8, 69.5, 69.5, 69.5, 69.1, 69.1,
69.0, 68.7, 68.6, 68.5, 68.4, 68.3, 68.2, 67.9, 67.8, 67.6,
67.5, 67.4, 63.2, 63.1, 63.1, 62.9, 62.9, 62.8, 62.7, 62.5,
62.4, 61.6, 61.5, 61.5, 60.3, 55.6 (C-2, 3, 4, 5, 6), 21.3,
20.9, 20.9, 20.8, 20.8, 20.7, 20.7, 20.6, 20.6, 20.6, 20.4,
20.4, 20.3, 14.1. Anal. Calcd for C253H242O99: C, 62.44;
H, 4.98. Found: C, 62.69; H, 5.08.
/
D
D
D
D
-
-
-
-
/
D-
/
D-
/
/
D-
/
D-
/
3.8. 4-Methoxyphenyl b-
glucopyranosyl-(106)]-a-
glucopyranosyl-(103)-[b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (9)
D
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranosyl-(10
-glucopyranosyl-(103)-[b-
-glucopyranosyl-(103)-b-
-glucopyranosyl-(106)]-b-
/
3)-[b-
3)-b-
6)]-a-
D-
/
D-
/
D
/
D-
/
D-
/
D
/
D-
/
/
3)-b-D
/
D-
/
D-
/
6)]-a-D
/
D-
/
3)-[b-
D
/
D-
Compound 7 (700 mg, 0.447 mmol) and 6 (1.20 g, 0.347
mmol) were dried together under high vacuum for 2 h,
then dissolved in anhyd CH2Cl2 (30 mL). TMSOTf (40
Compound 8 (800 mg, 0.164 mmol) was dissolved in a
satd solution of NH3 in MeOH (10 mL). After a week at
rt, the reaction mixture was concentrated, and the
residue was purified by chromatography on Sephadex
mL, 0.352 mmol) was added dropwise at ꢁ20 8C with
/
nitrogen 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
LH-20 (MeOH) to afford 9 (293 mg, 86.3%) as a foamy
1
solid: [a]D
ꢀ
/
22.18 (c 1.0, H2O); H NMR (D2O, 400
MHz): d 7.01Á
/
6.84 (dd, 4 H, MPC6H4ꢀ
/
), 5.19 (d, 3 H, J
3.2 Hz, 3 H-1), 4.68 (d, 1 H, J 8.0 Hz, H-1), 4.64 (d, 1 H,
J 8.0 Hz, H-1), 4.61 (d, 1 H, J 8.0 Hz, H-1), 4.58 (d, 1 H,
J 8.0 Hz, H-1), 4.37 (d, 1 H, J 8.0 Hz, H-1), 4.35 (d, 1 H,
with 1:1 petroleum etherÁ
/
EtOAc as the eluent gave the
32.48 (c
1.0, CHCl3); H NMR (CDCl3, 400 MHz): d 8.17Á7.17
(m, 100 H, 20 BzꢀH), 6.96Á6.84 (dd, 4 H, ꢀC6H4ꢀ),
5.92 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.91 (dd, 1 H,
J3,4 J4,5 9.7 Hz, H-4), 5.89 (dd, 1 H, J3,4 J4,5 9.7
Hz, H-4), 5.88 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.83
(dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.75 (dd, 1 H, J 2,3ꢃ
J3,4 9.7 Hz, H-3), 5.65Á5.58 (m, 4 H), 5.50 (dd, J1,2 7.9
Hz, J2,3 9.7 Hz, H-2), 5.42Á5.36 (m, 4 H), 5.22 (dd, 1 H,
J2,3 J3,4 9.7 Hz, H-3), 5.08 (dd, 1 H, J2,3 J3,4 9.7
Hz, H-3), 5.03 (d, 1 H, J1,2 7.9 Hz, H-1), 4.98 (dd, 1 H,
J3,4 J4,5 9.7 Hz, H-4), 4.94 (d, 2 H, J1,2 7.9 Hz, 2 H-
1), 4.85Á4.82 (m, 6 H), 4.82 (d, 1 H, J1,2 3.6 Hz, H-1),
4.82Á4.78 (m, 3 H), 4.76 (d, 1 H, J1,2 7.9 Hz, H-1), 4.75
(d, 1 H, J1,2 7.9 Hz, H-1), 4.64 (d, 1 H, J1,2 7.9 Hz, H-1),
4.62 (d, 1 H, J1,2 7.9 Hz, H-1), 4.62Á4.55 (m, 7 H), 4.53
(d, 1 H, J1,2 7.9 Hz, H-1), 4.52Á4.45 (m, 7 H), 4.31 (dd,
J5,6 3.1 Hz, J6,6 10.2 Hz, H-6), 4.25Á4.14 (m, 7 H), 4.06Á
3.88 (m, 15 H), 3.81 (s, 3 H, CH3O), 3.80Á3.72 (m, 5 H),
3.65 (m, 1 H), 3.50Á3.41 (m, 4 H), 2.44, 2.32, 2.29, 2.12,
product 8 (915 mg, 54.2%) as a syrup: [a]D
ꢀ
/
1
/
J 8.0 Hz, H-1), 4.33 (d, 1 H, J 8.0 Hz, H-1), 4.11Á
(m, 8 H), 3.83Á3.71 (m, 17 H), 3.68 (s, 3 H, CH3O),
3.67Á3.49 (m, 23 H), 3.38Á
3.12 (m, 26 H); 13C NMR
(D2O, 100 MHz): d 105.5, 105.5, 105.5, 105.5, 105.5,
105.5, 105.5, 105.5, 105.2 (9 C-1 for b bonds, JCꢀH
163.0, 164.3 Hz), 103.5, 101.9, 101.8 (3 C-1 for a bond,
JCꢀH 174.1 Hz) 78.6, 78.5, 78.5, 78.5, 78.3, 78.3, 78.3,
/4.00
/
/
/
/
ꢃ
/
ꢃ
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
ꢃ
/
ꢃ
/
/
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
78.3, 77.8, 76.2, 75.8, 75.8, 75.8, 75.3, 74.9, 74.9, 73.9,
73.9, 73.5, 73.5, 72.5, 72.5, 72.3, 72.3, 72.3, 72.3, 71.1,
71.0, 70.6, 70.5, 70.5, 70.4, 70.4, 63.4, 63.4, 63.4, 63.2,
63.2, 58.5, 58.5 (C-2, 3, 4, 5, 6). Anal. Calcd for
C79H128O62: C, 45.84; H, 6.19. Found: C, 46.03; H,
ꢃ
/
ꢃ
/
/
/
6.28. ESIMS for C79H128O62 (2068): 2091.5 [Mꢀ
/
Na]ꢀ.
/
/
3.9. 4-Methoxyphenyl 3-O-allyl-2,4,6-tri-O-acetyl-b-
D-
/
/
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranoside (10)
/
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)-]2,4-di-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-a-
3)-2,4,6-tri-O-acetyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b-
6)]-2,4-di-O-acetyl-b-
D-
D-
D-
D
-
/
/
D-
/
/
D-
2.09, 2.06, 2.04, 2.01, 1.97, 1.96, 1.95, 1.91, 1.90, 1.85,
1.81, 1.77, 1.74 (s, 51 H, 17 CH3CO); 13C NMR (CDCl3,
100 MHz): d 170.8, 170.6, 170.6, 170.6, 170.6, 170.4,
169.9, 169.5, 169.5, 169.4, 169.4, 169.3, 169.2, 169.2,
169.0, 169.0, 168.8 (17 C, 17 COCH3), 166.0, 166.0,
165.9, 165.9, 165.9, 165.8, 165.6, 165.6, 165.6, 165.6,
165.5, 165.1, 165.1, 165.1, 165.1, 165.0, 165.0, 165.0,
164.9, 164.9 (20 C, 20 COPh), 101.6, 101.5, 101.2, 100.9,
100.7, 100.4, 100.2, 100.0, 99.9, (9 C-1 for b bonds,
/
/
D-
/
D-
/
/
D-
/
D-
/
/
D-
JCꢀH
ꢃ
/
163.0Á
/
164.8 Hz), 94.2, 93.6, 93.5 (3 C-1 for a
bond, JCꢀH
73.6, 73.3, 73.1, 72.9, 72.7, 72.6, 72.6, 72.6, 72.5, 72.4,
ꢃ
/
172.0Á174.6 Hz), 78.3, 74.4, 74.4, 74.2,
/
Compound 1 (1.34 g, 1.12 mmol) and 6 (3.0 g, 0.867
mmol) were dried together under high vacuum for 2 h,
72.3, 72.2, 72.2, 72.2, 72.1, 72.0, 71.9, 71.9, 71.7, 71.7,

Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á
/2212
2209
then dissolved in anhyd CH2Cl2 (50 mL). TMSOTf (100
mL, 0.870 mmol) was added dropwise at ꢁ20 8C
with nitrogen protection. The reaction mixture
was stirred for 3 h, during which time the temperature
was gradually raised to ambient temperature. Then
he mixture was neutralized with Et3N. Concentration
of the reaction mixture, followed by purification on
29.8, 21.5, 21.0, 20.8, 20.6, 20.6, 20.4, 20.2. Anal. Calcd
for C234H236O98: C, 60.88; H, 5.12. Found: C, 61.05; H,
5.22.
/
3.10. 4-Methoxyphenyl 2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (11)
D-
/
D-
D-
D-
D
-
/
D-
a silica gel column with 1:2 petroleum etherÁ
/EtOAc
/
D-
as the eluent gave the product 10 (1.92 g, 48.1%) as
/
1
a syrup: [a]D
400 MHz): d 8.12Á
(dd, 4 H, MPC6H4ꢀ
H-4), 5.90 (dd, 1 H, J3,4
1 H, J3,4 J4,5 9.7 Hz, H-4), 5.82 (dd, 1 H, J3,4
J4,5 9.7 Hz, H-4), 5.79Á5.68 (m, 1 H, CH2ꢁCH ꢀ
CH2O), 5.64 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.63 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.60 (dd, 1 H,
J2,3 J3,4 9.7 Hz, H-3), 5.59 (dd, 1 H, J2,3 J3,4
ꢀ
/
28.68 (c 1.0, CHCl3); H NMR (CDCl3,
7.24 (m, 90 H, 16 BzꢀH), 6.94Á6.85
), 5.92 (dd, 1 H, J3,4 J4,5 9.7 Hz,
J4,5 9.7 Hz, H-4), 5.87 (dd,
/
D-
/
/
/
/
D-
/
/
ꢃ
/
ꢃ
/
/
D-
ꢃ
/
ꢃ
/
/
D-
ꢃ
/
ꢃ
/
ꢃ
/
/
ꢃ
/
/
/
/
/
D-
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
To a solution of 10 (1.8 g, 0.390 mmol) in MeOH (30
mL) was added PdCl2 (100 mg). After stirring for 3 h at
9.7 Hz, H-3), 5.49 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2),
5.43 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.40 (dd, J1,2
7.9 Hz, J2,3 9.7 Hz, H-2), 5.39 (dd, J1,2 7.9 Hz, J2,3
rt, TLC (1:2 petroleum etherÁEtOAc) indicated that the
/
reaction was complete. The mixture was filtered, the
solution was concentrated to dryness, and the resultant
residue was purified by flash chromatography (1:2
9.7 Hz, H-2), 5.24Á
/
5.14 (m, 3 H), 5.12Á/5.06 (m, 1 H,
CH2ꢁCH ꢀCH2O), 5.04 (dd, 1 H, J3,4
/
/
ꢃ
/
J4,5 9.7
ꢃ
/
petroleum etherÁ
a foamy solid: [a]D
(CDCl3, 400 MHz): d 8.09Á
6.95Á6.84 (dd, 4 H, MPC6H4ꢀ
J4,5 9.7 Hz, H-4), 5.89 (dd, 1 H, J3,4
H-4), 5.87 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.82 (dd, 1
H, J3,4 J4,5 9.7 Hz, H-4), 5.65 (dd, 1 H, J2,3 J3,4
9.7 Hz, H-3), 5.62 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.61 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.60 (dd, 1 H,
J2,3 J3,4 9.7 Hz, H-3), 5.50 (dd, J1,2 7.9 Hz, J2,3 9.7
/
EtOAc) to give 11 (1.43 g, 80.3%) as
Hz, H-4), 5.00 (d, 1 H, J1,2 7.9 Hz, H-1), 4.95 (d, 1 H,
1
ꢀ
/
20.28 (c 1.0, CHCl3); H NMR
7.26 (m, 90 H, 16 BzꢀH),
), 5.90 (dd, 1 H, J3,4
J4,5 9.7 Hz,
J1,2 7.9 Hz, H-1), 4.98 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2),
/
/
4.96 (dd, 1 H, J3,4
ꢃ/J4,5
ꢃ/9.7 Hz, H-4), 4.95 (dd,
/
/
ꢃ
/
1 H, J2,3 J3,4 9.7 Hz, H-3), 4.83 (d, 2 H, J1,2
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
3.6 Hz, 2 H-1), 4.81 (d, 1 H, J1,2 3.6 Hz, H-1), 4.79 (d,
ꢃ
/
ꢃ
/
1 H, J1,2 7.9 Hz, H-1), 4.76 (d, 1 H, J1,2 7.9 Hz, H-1),
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
4.76Á
(d, 1 H, J1,2 7.9 Hz, H-1), 4.59Á
H, J1,2 7.9 Hz, H-1), 4.49Á4.45 (m, 6 H), 4.44 (d, 1 H,
J1,2 7.9 Hz, H-1), 4.21 (dd, 1 H, J5,6 4.7 Hz, J6,6 12.4 Hz,
H-6), 4.19 (dd, 1 H, J5,6 5.1 Hz, J6,6 12.4 Hz, H-6), 4.15Á
4.10 (m, 6 H), 4.02Á3.88 (m, 13 H), 3.81 (s, 3 H, CH3O),
3.80Á3.74 (m, 7 H), 3.65Á3.40 (m, 7 H), 2.43, 2.34, 2.31,
/4.72 (m, 6 H), 4.64 (d, 1 H, J1,2 7.9 Hz, H-1), 4.60
ꢃ
/
ꢃ
/
/4.55 (m, 6 H), 4.52 (d, 1
ꢃ
/
ꢃ
/
ꢃ
/
ꢃ
/
/
Hz, H-2), 5.45 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.42
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.40 (dd, J1,2 7.9 Hz,
/
J2,3 9.7 Hz, H-2), 5.24Á/5.14 (m, 3 H), 5.02 (dd, 1 H,
/
J3,4 J4,5 9.7 Hz, H-4), 4.96 (d, 1 H, J1,2 7.9 Hz, H-1),
ꢃ
/
ꢃ
/
/
/
4.92 (d, 1 H, J1,2 7.9 Hz, H-1), 4.85 (d, 1 H, J1,2 3.6 Hz,
H-1), 4.82 (d, 2 H, J1,2 3.6 Hz, 2 H-1), 4.78 (d, 1 H,
2.11, 2.09, 2.08, 2.08, 2.06, 2.06, 2.05, 2.00, 1.97, 1.96,
1.95, 1.94, 1.94, 1.90, 1.89, 1.81, 1.78 (s, 60 H, 20
CH3CO); 13C NMR (CDCl3, 100 MHz): d 171.1, 171.0,
170.8, 170.8, 170.8, 170.6, 170.5, 170.4, 170.4, 170.0,
169.7, 169.5, 169.5, 169.4, 169.7, 169.2, 169.2, 168.9,
168.9, 168.9 (20 C, 20 COCH3), 166.2, 166.2, 166.1,
166.1, 166.0, 165.8, 165.6, 165.6, 165.6, 165.5, 165.2,
165.2, 165.1, 165.1, 165.0, 165.0 (16 C, 16 COPh), 101.8,
101.6, 101.5, 100.9, 100.5, 100.4, 100.3, 100.1, 99.8 (9 b-
C-1), 94.5, 94.1, 93.6 (3 a-C-1), 78.5, 75.8, 75.4, 75.3,
75.0, 74.9, 74.4, 74.1, 73.6, 72.9, 72.6, 72.6, 72.6, 72.5,
72.4, 72.4, 72.4, 72.2, 72.2, 72.1, 72.0, 71.9, 71.8, 71.8,
71.6, 71.6, 70.8, 70.5, 69.8, 69.7, 69.5, 69.3, 69.3, 69.2,
69.1, 69.0, 68.4, 68.4, 68.1, 68.1, 68.1, 67.9, 67.7, 62.9,
62.9, 62.5, 62.1, 61.5, 61.5, 60.6, 55.8 (C-2, 3, 4, 5, 6),
J1,27.9 Hz, H-1), 4.76 (d, 1 H, J1,2 7.9 Hz, H-1), 4.76Á
4.72 (m, 6 H), 4.66 (d, 1 H, J1,2 7.9 Hz, H-1), 4.61 (d, 1
H, J1,2 7.9 Hz, H-1), 4.59Á4.56 (m, 6 H), 4.55 (d, 1 H,
J1,2 7.9 Hz, H-1), 4.52Á4.48 (m, 10 H), 4.46 (d, 1 H, J1,2
7.9 Hz, H-1), 4.23 (dd, 1 H, J5,6 4.7 Hz, J6,6 12.4 Hz, H-
6), 4.21 (dd, 1 H, J5,6 5.1 Hz, J6,6 12.4 Hz, H-6), 4.15Á
4.10 (m, 6 H), 4.02Á3.88 (m, 10 H), 3.81 (s, 3 H, CH3O),
3.80Á3.74 (m, 6 H), 3.65Á3.40 (m, 7 H), 2.43, 2.34, 2.31,
/
/
/
/
/
/
/
2.11, 2.09, 2.08, 2.08, 2.06, 2.06, 2.05, 2.00, 1.97, 1.96,
1.95, 1.94, 1.94, 1.90, 1.89, 1.81, 1.78 (s, 60 H, 20
CH3CO); 13C NMR (CDCl3, 100 MHz): d 171.1, 171.0,
170.8, 170.8, 170.8, 170.6, 170.5, 170.4, 170.4, 170.0,
169.7, 169.5, 169.5, 169.4, 169.7, 169.2, 169.2, 168.9,
168.9, 168.9 (20 C, 20 COCH3), 166.2, 166.2, 166.1,
166.1, 166.0, 165.8, 165.6, 165.6, 165.6, 165.5, 165.2,

2210
Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á2212
/
165.2, 165.1, 165.1, 165.0, 165.0 (16 C, 16 COPh), 101.8,
101.6, 101.5, 100.9, 100.5, 100.4, 100.3, 100.1, 99.8 (9 b-
C-1), 94.5, 94.1, 93.6 (3 a-C-1), 78.5, 75.8, 75.4, 75.3,
75.0, 74.9, 74.4, 74.1, 73.6, 72.9, 72.6, 72.6, 72.6, 72.5,
72.4, 72.4, 72.4, 72.2, 72.2, 72.1, 72.0, 71.9, 71.8, 71.8,
71.6, 71.6, 70.8, 70.5, 69.8, 69.7, 69.5, 69.3, 69.3, 69.2,
69.1, 69.0, 68.4, 68.4, 68.1, 68.1, 68.1, 67.9, 67.7, 62.9,
62.9, 62.5, 62.1, 61.5, 61.5, 60.6, 55.8 (C-2, 3, 4, 5, 6),
29.8, 21.5, 21.0, 20.8, 20.6, 20.6, 20.4, 20.2. Anal. Calcd
for C231H232O98: C, 66.54; H, 5.16. Found: C, 66.82; H,
5.23.
(d, 1 H, J1,2 7.9 Hz, H-1), 4.54Á
J5,6 3.1 Hz, J6,6 10.2 Hz, H-6), 4.25Á
(s, 3 H, CH3O), 3.80Á3.72 (m, 6 H), 3.62 (m, 1 H), 3.50Á
/
4.42 (m, 10 H), 4.30 (dd,
/4.13 (m, 15 H), 3.81
/
/
3.41 (m, 6 H), 2.43, 2.33, 2.32, 2.27, 2.11, 2.09, 2.05,
2.05, 2.04, 2.00, 1.95, 1.95, 1.90, 1.90, 1.90, 1.89, 1.84,
1.81, 1.80, 1.76, 1.74, 1.73 (s, 66 H, 22 CH3CO); 13C
NMR (CDCl3, 100 MHz): d 170.9, 170.7, 170.7, 170.7,
170.6, 170.6, 170.5, 170.4, 170.0, 169.5, 169.5, 169.4,
169.4, 169.3, 169.3, 169.2, 169.2, 169.1, 169.1, 169.0,
169.0, 168.8 (22 C, 22 COCH3), 166.1, 166.0, 166.0,
166.0, 166.0, 165.9, 165.9, 165.9, 165.8, 165.8, 165.6,
165.6, 165.6, 165.6, 165.5, 165.1, 165.1, 165.1, 165.1,
165.0, 165.0, 165.0, 164.9, 164.9 (24 C, 24 COPh), 101.6,
101.5, 101.4, 101.2, 100.9, 100.7, 100.6, 100.4, 100.2,
3.11. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (12)
D-
/
D-
100.0, 99.8 (11 C-1 for b bonds, JCꢀH
Hz), 94.2, 94.2, 93.7, 93.5 (4 C-1 for a bond, JCꢀH
172.0Á174.6 Hz), 78.6, 74.4, 74.4, 74.2, 74.2, 73.6, 73.2,
ꢃ
/
163.0Á164.8
/
/
D-
ꢃ
/
/
D-
/
/
D
D
D
D
-
-
-
-
73.2, 72.9, 72.7, 72.6, 72.6, 72.6, 72.5, 72.4, 72.3, 72.2,
72.2, 72.2, 72.1, 72.1, 72.0, 71.9, 71.9, 71.7, 71.7, 71.6,
71.1, 71.0, 71.0, 71.0, 70.6, 70.5, 69.8, 69.5, 69.5, 69.5,
69.4, 69.4, 69.1, 69.1, 69.0, 68.7, 68.6, 68.5, 68.4, 68.3,
68.2, 67.9, 67.8, 67.6, 67.5, 67.4, 63.2, 63.1, 63.1, 63.0,
62.9, 62.9, 62.8, 62.8, 62.7, 62.5, 62.4, 61.8, 61.6, 61.5,
61.5, 60.3, 55.6 (C-2, 3, 4, 5, 6), 29.6, 21.3, 20.9, 20.9,
20.8, 20.8, 20.7, 20.7, 20.6, 20.6, 20.6, 20.4, 20.4, 20.4,
20.3, 14.1. Anal. Calcd for C309H298O123: C, 62.07; H,
4.99. Found: C, 62.31; H, 5.16.
/
D-
/
D-
/
/
D-
/
D-
/
/
D-
/
D-
/
/
D-
3.12. 4-Methoxyphenyl b-
glucopyranosyl-(106)]-a-
glucopyranosyl-(103)-[b-
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
glucopyranosyl-(10
D
-glucopyranosyl-(10
-glucopyranosyl-(103)-b-
-glucopyranosyl-(106)]-a-
-glucopyranosyl-(103)-[b-
-glucopyranosyl-(103)-b-
-glucopyranosyl-(106)]-a-
-glucopyranosyl-(103)-[b-
6)]-b-D-glucopyranoside (13)
/
3)-[b-D-
Compound 7 (500 mg, 0.319 mmol) and 11 (1.2 g, 0.262
mmol) were dried together under high vacuum for 2 h,
then dissolved in anhyd CH2Cl2 (30 mL). TMSOTf (30
/
D
/
D-
/
D
/
D-
/3)-b-
D
/
D-
mL, 0.265 mmol) was added dropwise at ꢁ20 8C with
/
/6)]-a-
D
/
D-
nitrogen 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
/3)-[b-
D
/
D-
/3)-b-
D
/
D-
/
Compound 12 (500 mg, 0.084 mmol) was dissolved in a
satd solution of NH3 in MeOH (10 mL). After a week at
rt, the reaction mixture was concentrated, and the
residue was purified by chromatography on Sephadex
LH-20 (MeOH) to afford 13 (184 mg, 85.8%) as a foamy
with 1:2.5 petroleum etherÁ
/
EtOAc as the eluent gave
30.68
(c 1.0, CHCl3); H NMR (CDCl3, 400 MHz): d 8.17Á
7.17 (m, 120 H, 24 BzꢀH), 6.96Á6.83 (dd, 4 H,
MPC6H4ꢀ), 5.93Á5.84 (m, 5 H), 5.84 (dd, 1 H, J3,4
J4,5 9.7 Hz, H-4), 5.82 (dd, 1 H, J3,4 J4,5 9.7 Hz,
H-4), 5.74 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.66Á5.57
(m, 7 H), 5.50 (dd, J1,2 7.9 Hz, J2,3 9.8 Hz, H-2), 5.42Á
5.32 (m, 6 H), 5.20 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.08 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.00 (d, 1 H, J1,2
7.9 Hz, H-1), 4.98 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4),
4.95 (d, 3 H, J1,2 7.9 Hz, 3 H-1), 4.89Á4.84 (m, 3 H), 4.83
(d, 1 H, J1,2 3.6 Hz, H-1), 4.82 (d, 2 H, J1,2 3.6 Hz, H-1),
4.82Á4.76 (m, 15 H), 4.76 (d, 1 H, J1,2 7.9 Hz, H-1), 4.75
(d, 1 H, J1,2 7.9 Hz, H-1), 4.64 (d, 1 H, J1,2 7.9 Hz, H-1),
4.62 (d, 1 H, J1,2 7.9 Hz, H-1), 4.62Á4.56 (m, 15 H), 4.55
the product 12 (668 mg, 42.7%) as a syrup: [a]D
ꢀ
/
1
/
/
/
/
/
ꢃ
/
solid: [a]D
MPC6H4ꢀ
J 7.8 Hz, H-1), 4.69 (d, 5 H, J 7.8 Hz, 5 H-1), 4.45 (d, 4
H, J 7.8 Hz, 4 H-1), 4.21Á4.18 (m, 10 H), 3.94Á3.80 (m,
ꢀ
/
26.28 (c 1.0, H2O): d 7.11Á
/
6.94 (dd, 4 H,
ꢃ
/
ꢃ
/
ꢃ
/
/), 5.29 (d, 4 H, J 3.2 Hz, 4 H-1), 5.04 (d, 1 H,
ꢃ
/
ꢃ
/
/
/
/
/
ꢃ
/
ꢃ
/
22 H), 3.78 (s, 3 H, CH3O), 3.77Á
/
3.52 (m, 26 H), 3.45Á
/
ꢃ
/
ꢃ
/
3.22 (m, 33 H); 13C NMR (D2O, 100 MHz): d 105.4,
105.4, 105.4, 105.4, 105.4, 105.4, 105.4, 105.4, 105.4,
ꢃ
/
ꢃ
/
/
105.4, 105.2, (11 C-1 for b bonds, JCꢀH
Hz), 103.4, 101.8, 101.7, 101.7 (4 C-1 for a bond,
JCꢀH 174.1 Hz), 85.6, 85.3, 84.5, 78.6, 78.6, 78.5, 78.5,
ꢃ163.0, 164.3
/
/
ꢃ
/
78.5, 78.2, 78.2, 78.2, 78.2, 77.7, 76.1, 75.8, 75.8, 75.8,
75.8, 75.3, 74.8, 74.8, 74.8, 74.8, 73.8, 73.8, 73.8, 73.4,
/

Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á
/2212
2211
73.4, 72.5, 72.5, 72.5, 72.2, 72.2, 72.2, 72.2, 72.2, 71.0,
71.0, 70.6, 70.5, 70.5, 70.4, 70.4, 70.3, 70.3, 63.4, 63.4,
63.4, 63.4, 63.2, 63.2, 58.5 (C-2, 3, 4, 5, 6), 32.8, 32.8,
32.5. Anal. Calcd for C97H158O77: C, 45.58; H, 6.19.
Found: C, 45.76; H, 6.28. ESIMS for C97H158O77
20.5, 20.4. Anal. Calcd for C141H130O51: C, 64.14; H,
4.93. Found: C, 64.34; H, 5.02.
3.14. 2,3,4,6-Tetra-O-benzoyl-b-
3)-[2,3,4,6-tetra-O-benzoyl-b- -glucopyranosyl-(10
2,4-di-O-acetyl-a- -glucopyranosyl-(103)-2,4,6-tri-O-
acetyl-b- 3)-[2,3,4,6-tetra-O-
-glucopyranosyl-(10
benzoyl-b- 6)]-2,4-di-O-acetyl-a-
-glucopyranosyl-(10
glucopyranosyl trichloroacetimidate (15)
D
-glucopyranosyl-(10
/
D
/
6)]-
(2554): 2577.0 [Mꢀ
Na]ꢀ.
/
D
/
D
/
D
/
D-
3.13. 4-Methoxyphenyl 2,3,4,6-tri-O-benzoyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-a-
glucopyranosyl-(103)-2,4,6-tri-O-acetyl-b-
glucopyranosyl-(103)-[2,3,4,6-tetra-O-benzoyl-b-
glucopyranosyl-(106)]-2,4-di-O-acetyl-b-
glucopyranoside (14)
D-
/
D
-
-
Compound 14 (400 mg, 0.152 mmol) was dissolved 4:1
CH3CNÁH2O (1 mL), and then (NH4)2Ce(NO3)6 (50
mg) was added. After stirring the mixture for 3 h at rt,
TLC (1:1 petroleum etherÁEtOAc) indicated that the
/
D-
/
/
D-
/
D
/
/
D-
reaction was complete. The mixture was filtered, the
solution was concentrated to dryness, and the resultant
residue was purified by flash chromatography (1.5:1
Compound 7 (450 mg, 0.287 mmol) and 2 (300 mg,
0.243 mmol) were dried together under high vacuum for
2 h, then dissolved in anhyd CH2Cl2 (10 mL). TMSOTf
petroleum etherÁ
/
EtOAc) to give the hexasaccharide
17.68 (c
1.0, CHCl3); H NMR (CDCl3, 400 MHz): d 8.06Á7.25
(m, 60 H, 12 BzꢀH), 5.93 (dd, 1 H, J3,4 J4,5 9.7 Hz,
H-4), 5.91 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.85 (dd, 1
H, J3,4 J4,5 9.7 Hz, H-4), 5.77 (dd, 1 H, J2,3 J3,4
9.7 Hz, H-3), 5.73 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.51 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.47 (dd, J1,2 7.9
hemiacetal (322 mg, 83.6%) as a syrup: [a]D
ꢀ
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1
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(15 mL, 0.132 mmol) was added dropwise at ꢁ20 8C
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ꢃ
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with nitrogen 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
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Hz, J2,3 9.7 Hz, H-2), 5.36 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz,
H-2), 5.34 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.01 (d, 1
H, J1,2 7.9 Hz, H-1), 4.97 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-
gel column with 1:1 petroleum etherÁ/EtOAc as the
eluent gave the product 14 (471 mg, 73.4%) as a foamy
1
solid: [a]D
400 MHz): d 8.12Á
(dd, 4 H, MPC6H4ꢀ
H-4), 5.89 (dd, 1 H, J3,4
H, J3,4 J4,5 9.7 Hz, H-4), 5.67 (dd, 1 H, J2,3
9.7 Hz, H-3), 5.62 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.59 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.49 (dd, J1,2 7.9
ꢀ
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18.98 (c 1.0, CHCl3); H NMR (CDCl3,
7.26 (m, 60 H, 12 BzꢀH), 6.98Á6.85
), 5.91 (dd, 1 H, J3,4 J4,5 9.7 Hz,
J4,5 9.7 Hz, H-4), 5.82 (dd, 1
J3,4
2), 4.95 (dd, 1 H, J3,4
3.6 Hz, J2,3 9.7 Hz, H-2), 4.92 (d, 1 H, J1,2 7.9 Hz, H-1),
ꢃ/J4,5
ꢃ9.7 Hz, H-4), 4.94 (dd, J1,2
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4.86 (d, 1 H, J1,2 3.6 Hz, H-1), 4.66 (d, 1 H, J1,2 7.9 Hz,
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H-1), 4.58Á
H, J1,2 7.9 Hz, H-1), 4.37 (d, 1 H, J1,2 7.9 Hz, H-1), 4.32
(dd, 1 H, J5,6 4.7 Hz, J6,6 12.4 Hz, H-6), 4.22Á4.10 (m, 7
H), 4.08Á4.00 (m, 1 H), 3.94Á3.84 (m, 6 H), 3.71Á3.56
(m, 2 H), 3.41Á3.36 (m, 1 H), 2.39, 2.04, 2.02, 1.99, 1.87,
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4.53 (m, 5 H), 4.52Á/4.45 (m, 4 H), 4.42 (d, 1
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Hz, J2,3 9.7 Hz, H-2), 5.41 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz,
H-2), 5.39 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.03 (d, 1
H, J1,2 7.9 Hz, H-1), 4.98 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-
/
1.78, 1.62 (s, 21 H, 7 CH3CO); 13C NMR (CDCl3, 100
MHz): d 170.5, 170.0, 169.8, 169.5, 169.5, 169.3, 169.1
(7 C, 7 COCH3), 166.2, 165.9, 165.9, 165.9, 165.7, 165.7,
165.5, 165.2, 165.1, 165.4, 164.9, 164.8 (12 C, 12 COPh),
102.3, 101.4, 101.0, 100.3, 99.8, 93.0 (C-1), 75.2, 74.3,
73.2, 72.8, 72.8, 72.6, 72.5, 72.5, 72.2, 72.1, 72.1, 71.9,
71.9, 71.7, 71.5, 71.0, 70.5, 70.3, 69.5, 69.2, 68.8, 68.7,
68.2, 68.0, 62.7, 62.6, 62.5, 62.4, 61.5 (C-2, 3, 4, 5, 6),
29.6, 22.6, 21.4, 20.6, 20.6, 20.5, 20.4, 20.3. Anal. Calcd
for C134H124O50: C, 63.51; H, 4.90. Found: C, 63.80; H,
5.00.
2), 4.96 (dd, 1 H, J3,4
ꢃ
/
J4,5
ꢃ9.7 Hz, H-4), 4.95 (dd, J1,2
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3.6 Hz, J2,3 9.7 Hz, H-2), 4.93 (d, 1 H, J1,2 7.9 Hz, H-1),
4.85 (d, 1 H, J1,2 3.6 Hz, H-1), 4.66 (d, 1 H, J1,2 7.9 Hz,
H-1), 4.58Á
H, J1,2 7.9 Hz, H-1), 4.38 (d, 1 H, J1,2 7.9 Hz, H-1), 4.32
(dd, 1 H, J5,6 4.7 Hz, J6,6 12.4 Hz, H-6), 4.18Á4.03 (m, 6
H), 4.05Á3.84 (m, 5 H), 3.81(s, 3 H, CH3O), 3.60Á3.56
(m, 1 H), 3.42Á3.40 (m, 1 H), 2.39, 2.10, 2.00, 1.99, 1.85,
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4.53 (m, 5 H), 4.52Á
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4.45 (m, 5 H), 4.41 (d, 1
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1.82, 1.62 (s, 21 H, 7 CH3CO); 13C NMR (CDCl3, 100
MHz): d 170.4, 170.1, 169.6, 169.4, 169.4, 169.3, 168.7
(7 C, 7 COCH3), 166.0, 166.0, 165.9, 165.9, 165.8, 165.6,
165.6, 165.5, 165.1, 165.1, 164.9, 164.9 (12 C, 12 COPh),
101.4, 101.1, 100.6, 100.4, 99.8 (5 b-C-1), 93.0 (a-C-1),
78.4, 75.5, 74.5, 73.1, 72.9, 72.9, 72.7, 72.6, 72.4, 72.2,
72.1, 72.1, 72.0, 71.9, 71.6, 71.1, 71.0, 70.4, 69.5, 69.5,
69.5, 69.3, 68.8, 68.6, 68.2, 67.9, 67.8, 62.9, 62.6, 62.4,
61.4, 55.6 (C-2, 3, 4, 5, 6), 29.6, 21.2, 20.7, 20.6, 20.5,
The hemiacetal was dissolved in CH2Cl2 (10 mL),
then CCl3CN (0.05 mL, 1.0 mmol) and K2CO3 (500 mg,
3.5 mmol) was added. The reaction mixture was stirred
for 10 h, at the end of which time TLC (1.5:1 petroleum
etherÁEtOAc) indicated that the reaction was complete.
/
The mixture was filtered, and the filtrate was concen-
trated. The residue was purified by flash chromatogra-
phy (1.5:1 petroleum etherÁ
86.7%) as a foamy solid: [a]D
/
EtOAc) to give 15 (295 mg,
26.98 (c 1.0, CHCl3); 1H
ꢀ
/

2212
Z. Wu et al. / Carbohydrate Research 338 (2003) 2203Á2212
/
NMR (CDCl3, 400 MHz): d 8.44 (s, 1 H, Cꢁ
8.05Á7.27 (m, 60 H, 12 BzꢀH), 6.32 (d, 1 H, J1,2 3.6 Hz,
H-1), 5.92 (dd, 1 H, J3,4 J4,5 9.7 Hz, H-4), 5.90 (dd, 1
H, J3,4 J4,5 9.7 Hz, H-4), 5.87 (dd, 1 H, J3,4 J4,5
9.7 Hz, H-4), 5.83 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3),
5.78 (dd, 1 H, J2,3 J3,4 9.7 Hz, H-3), 5.65 (dd, 1 H,
J2,3 J3,4 9.7 Hz, H-3), 5.50 (dd, J1,2 7.9 Hz, J2,3 9.7
/
NH),
Acknowledgements
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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).
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Hz, H-2), 5.37 (dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.40
(dd, J1,2 7.9 Hz, J2,3 9.7 Hz, H-2), 5.00 (d, 1 H, J1,2 7.9
References
Hz, H-1), 4.97 (dd, 1 H, J3,4
(dd, J1,2 3.6 Hz, J2,3 9.7 Hz, H-2), 4.92 (d, 1 H, J1,2 7.9
Hz, H-1), 4.86 (d, 1 H, J1,2 3.6 Hz, H-1), 4.57(d, 1 H, J1,2
ꢃ
/
J4,5
ꢃ9.7 Hz, H-4), 4.94
/
1. Yang, G.; Kong, F. Synlett 2000, 1423Á
2. Ning, J.; Zhang, W.; Yi, Y.; Yang, G.; Wu, Z.; Yi, J.; Kong,
F. Bioorg. Med. Chem. 2003, 11, 2193Á2203.
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1426.
7.9 Hz, H-1), 4.58Á
4.42 (d, 1 H, J1,2 7.9 Hz, H-1), 4.38 (d, 1 H, J1,2 7.9 Hz,
H-1), 4.30 (dd, 1 H, J5,6 4.7 Hz, J6,6 12.4 Hz, H-6), 4.22Á
4.10 (m, 6 H), 3.96Á3.75 (m, 6 H), 3.68Á3.49 (m, 3 H),
3.43Á3.37 (m, 2 H), 2.36, 2.04, 2.02, 2.00, 1.86, 1.82, 1.63
/
4.53 (m, 5 H), 4.52Á/4.45 (m, 4 H),
/
/
/
/
/
/
/
(s, 21 H, 7 CH3CO); 13C NMR (CDCl3, 100 MHz): d
170.4, 170.0, 169.5, 169.5, 169.4, 169.3, 169.0 (7 C, 7
COCH3), 166.0, 165.9, 165.9, 165.7, 165.7, 165.5, 165.3,
165.2, 165.1, 165.0, 164.9, 164.9 (12 C, 12 COPh), 101.3,
101.0, 100.9, 100.6 (4 b-C-1), 93.1, 92.8 (2 a-C-1), 76.1,
74.3, 73.1, 72.9, 72.7, 72.6, 72.3, 72.2, 72.1, 72.0, 71.9,
71.8, 71.6, 71.6, 71.5, 71.2, 70.9, 70.4, 69.7, 69.2, 68.9,
68.1, 68.1, 67.8, 67.6, 63.0, 62.5, 61.3, 60.3 (C-2, 3, 4, 5,
6), 29.6, 22.6, 20.9, 20.9, 20.7, 20.6, 20.5, 20.3. Anal.
Calcd for C136H124Cl3NO50: C, 60.98; H, 4.63. Found:
C, 61.23; H, 4.81.
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/
/
7. Ogawa, T.; Yamamoto, H. Carbohydr. Res. 1985, 137, 79Á
/
88.
8. (a) Ning, J.; Yi, Y.; Kong, F. Tetrahedron Lett. 2002,
5545Á
(b) Ning, J.; Lin, B.; Lei, H.; Kong, F. J. Agric. Food Chem.
2003, 51, 987Á991.
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5549;
/