Synthesis of a potential tetrasaccharide ligand for E-selectin

Article abstract of DOI:10.1016/S0008-6215(02)00028-9

A potential tetrasaccharide ligand for E-selectin, (Na^+-O₃SO-3)Galβ-(1→4) [Fucα-(1→3)]Glcβ-(1→6)Gal, an analogue of the ovarian cystadenoma glycoprotein tetrasaccharide fragment, was synthesized in a highly practical way.

Full text of DOI:10.1016/S0008-6215(02)00028-9

Carbohydrate Research 337 (2002) 621–628
www.elsevier.com/locate/carres
Note
Synthesis of a potential tetrasaccharide ligand for E-selectin
Zhi-Hui Qin, Hong Liu, Hui Li, Meng-Shen Cai, Zhong-Jun Li*
National Research Laboratory of Natural and Biomimetic Drugs, Department of Chemical Biology, School of Pharmaceutical Sciences,
Peking Uni6ersity, Beijing 100083, PR China
Received 1 October 2001; received in revised form 16 January 2002; accepted 17 January 2002
Abstract
A potential tetrasaccharide ligand for E-selectin, (Na+ −O3SO-3)Galb-(1“4)[Fuca-(1“3)]Glcb-(1“6)Gal, an analogue of the
ovarian cystadenoma glycoprotein tetrasaccharide fragment, was synthesized in a highly practical way. © 2002 Elsevier Science
Ltd. All rights reserved.
Keywords: Potential selectin ligand; Tumor-related oligosaccharides; Oligosaccharide; Synthesis
1. Introduction
to prepare, and preserve the binding affinities and
specificities of the original structure is very important
for the development of sLex/a based selectin antago-
nists. Previous structure–activity relationship (SAR)
studies showed that the acetylated amino group of the
GlcNAc residue was not essential for the interaction
with selectins, and replacement of the core glucosamine
residue of sLex and sLea with glucose was found to
have little or no effect on selectin recognition.6a,b From
this point of view, we replaced GlcNAc by glucose,
since the substitution greatly facilitates the synthesis by
eliminating the need for troublesome nitrogen protec-
tion/deprotection and without sacrifice of the expected
biological activity. We report here a highly practical
synthesis of the tetrasaccharide (Na+ −O3SO-3)Galb-
(1“4)[Fuca-(1“3)]Glcb-(1“6)Gal, an analogue of
the ovarian cystadenoma glycoprotein tetrasaccharide
fragment having E-selectin-binding activity.
The role of carbohydrates in cell-adhesion processes,
specifically, the interaction between the selectins and
the Lewis sugars or their derivatives, has led to exten-
sive studies in both biology and chemistry.1,2 Following
their reports that disclosed the isolation of a mixture of
two sulfated tetrasaccharides from an ovarian cystade-
noma glycoprotein which exhibited E-selectin-binding
properties comparable to those of sialylated com-
pounds,3 Chai et al.4 reported another group of strong
E-selectin-binding oligosaccharide components released
from the same source (Fig. 1). In structure b, bianten-
nary sulfated Lewisa/x components were attached to
galactose via b-(1“3) or b-(1“6) glycosidic bonds,
and Nicolaou et al.5 have reported the synthesis of the
tetrasaccharide with b-(1“3)-linked galactose at the
reducing terminal of sulfated Lea/x
.
In our studies on tumor-related oligosaccharides, we
focused our attention on another tetrasaccharide frag-
ment of the foregoing structure in which b-(1“6)-
linked galactose was attached to the reducing end of
sulfated Lex, e.g., (Na+ −O3SO-3) Galb-(1“4)[Fuca“
(1“3)]GlcNAcb-(1“6)Gal. Meanwhile, simplification
of sLex/a sugars to analogues that are inexpensive, easy
Fig. 1. Oligosaccharide components released from ovarian
cystadenoma glycoprotein.
* Corresponding author. Fax: +86-10-62367134.
E-mail address: zjli@mail.bjmu.edu.cn (Z.-J. Li).
0008-6215/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(02)00028-9

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Z.-H. Qin et al. / Carbohydrate Research 337 (2002) 621–628
The linear trisaccharide skeleton 6 was constructed
with the glycosyl acceptor 4 and acetylated lactosyl
bromide under activation by 1:1 Ag2CO3–AgOTf in
high yield (Scheme 2). A small amount of trans-acety-
lation product 7 was also isolated as byproduct. In
the following steps, the selective protection of the lac-
tose portion to allow the 3-OH of glucose to remain
free is the key step in our work. Hasegawa et al.10
have developed an effective and interesting selective
benzoylation method to achieve this goal in which
3%,4%-O-isopropylidenelactose was used as starting ma-
terial, and these reaction conditions were later opti-
mized by Kondo et al.11. However, whether this
reaction can still work well with the more compli-
cated lactose-containing oligosaccharide substrate re-
mains unknown.
Scheme 1. Synthesis of glycosyl acceptor 4. (a) TrCl, DMAP;
(b) NaH, BnBr; (c) formic acid–ether; (d) NaOMe 80% (three
steps).
2. Results and discussion
In our work, trisaccharide 6 was first deacetylated
and then isopropylidenated at the 3,4-OH of the lac-
tose portion according to Catelani’s method12 to ob-
tain the benzoylation substrate. Selective benzoylation
was performed following Kondo’s procedure and one
main product, together with a minor one, were iso-
lated from the crude product. From their mass spec-
tra, it was easy to deduce that the minor one was the
perbenzoylation product, while the main one had the
correct molecular weight, namely leaving one hydroxy
group free, as expected. However the position of ben-
zoylation had to be confirmed since the substrate we
used was a trisaccharide. Owing to the higher reactiv-
ity of 6-OH compared with that of 2-OH or 3-OH,
there are in theory three possible selective benzoyla-
tion patterns for the trisaccharide 8 (Scheme 3).
For the galactose at the reducing end, the anomeric
center was masked by a 4-methoxyphenyl (Mp) group,7
which can either be maintained in the final deprotective
product or be removed selectively under mild condi-
tions. The galactose derivatives 17 was treated with
chlorotriphenylmethane in pyridine–dichloromethane
in the presence of DMAP8 to afford the 6-trityl deriva-
tive 2, which was peralkylated with benzyl bromide to
generate 3. Removing the trityl group with formic acid
in ether9 led to the formation of 4 and a significant
amount of formylated byproduct 5 (about 20% of the
product was formylated, as judged by column chro-
matography) which could be converted back into the
desired glycosyl acceptor 4 by treating the crude
product with sodium methoxide (Scheme 1).
Scheme 2. Synthesis of the trisaccharide skeleton and its selective benzyolation. (a) 1:1 Ag2CO3–AgOTf, CH2Cl2, 0 °C, 83%; (b)
,
(i) NaOMe–MeOH; (ii) camphorsulfonic acid, 4 A molecular sieves, 2,2-dimethoxypropane, rt, 24 h.; (iii) NEt3; 10:1 MeOH–
H2O, 100 °C, 5 h, 71% (three steps); (c) BzCl, toluene–pyridine, 0 °C 65.4%.
Scheme 3. Three possible selective benzoylation patterns.

Z.-H. Qin et al. / Carbohydrate Research 337 (2002) 621–628
623
Scheme 4. Synthesis of the target tetrasaccharide. (a) CuBr2–Bu4N+Br−, ClCH2CH2Cl–DMF, rt, 48 h. 70.8%; (b) (i) 20% Pd–C,
H2, MeOH–dioxane, rt, 20 h; (ii) Ac2O–Py, DMAP 71.8%; (c) TsOH·H2O, EtOAc, rt, 69.2%; (d) (i) CH3C(OMe)3, TsOH·H2O;
(ii) 80% HOAc, rt 90% (two steps); (e) SO3·Py complex, DMF, rt quantitative yield; (f) NaOMe–MeOH, 64.5%
1
In the H NMR spectrum of the main product, two
hexose hydrogen atoms underwent significant downfield
shifts, to 5.35 and 5.18 ppm, respectively, due to their
3. Experimental
General methods.—All reactions were monitored by
TLC on Silica Gel GF254. Column chromatography was
performed using Silica Gel H60. All solvents were dried
and/or distilled before use. Melting points were deter-
mined with a X4 apparatus and are uncorrected. Opti-
cal rotations were measured at rt with an AA-10R
(Optical Activity Co., Ltd) polarimeter. NMR spectra
were recorded (internal standard tetramethylsilane)
with a Bruker ARX-400 or Jeol-300 type spectrometer
using CDCl3 as the solvent. Elemental analyses
were performed on a Perkin–Elmer 240C instrument.
MALDI-TOF were recorded on a LDI-1700 instru-
ment.
acylation. In the H,1H-COSY NMR spectrum, these
1
two hydrogen atoms correlate with an anomeric proton,
indicating that they are 2%-H and 2%%-H of the lactose
portion. Thus, B represents the structure of the main
product, which is also the structure we desired.
In the next step, the perbenzylated
L-fucose ethyl
thioglycoside13 was employed as the glycosyl donor to
couple with the selective benzoylation product 9 under
activation by CuBr2–NBu4Br,14 affording compound
11. About 10% of the glycosyl donor self-coupled to
afford difucose 12 as a byproduct. Based on the differ-
ent chemical shifts (5.20 and 4.50 ppm) and coupling
constants (3.3 and 7.8 Hz) of the two anomeric hydro-
gen atoms, it is interesting that the two fucose residues
has different configurations at their anomeric centers
(Scheme 4).
4-Methoxyphenyl 2,3,4-tri-O-benzyl-i-
ranoside (4) and 4-methoxyphenyl 2,3,4-tri-O-benzyl-6-
O-formyl-i- -galactopyranoside (5).—4-Methoxy-
phenyl 2,3,4-tri-O-benzyl-6-O-trityl-b- -galactopyran-
D-galactopy-
D
D
oside (3, 8.5 g, 10.6 mmol) was dissolved in 1:1 Et2O–
formic acid (80 mL) and stirred at rt for 8 h. After
dilution with Et2O (200 mL), the mixture was washed
with water (5×30 mL) and the aqueous phase back-ex-
tracted with Et2O. The organic phase was combined and
washed with satd NaHCO3, and dried with MgSO4.
After concentration, the residue was dissolved in 1:1
CHCl3–MeOH (70 mL) and NaOMe (300 mg) was
added. The mixture was stirred at rt for 1 h, and then
neutralized with cationic resin (H+). The solution was
concentrated and the residue purified with silica-gel
chromatography (4:1 acetone–light petroleum) to give
compound 4 as white needles (4.5 g, 80%), mp 123–
125 °C, [h]D −20.5° (c 0.39, CH2Cl2); Rf 0.35 (1:3
acetone–light petroleum); 1H NMR (400 MHz, CDCl3):
7.26–7.35 (m, 15 H, ArH), 6.76–6.97 (4 H, AA%BB%,
Mp), 4.64–5.00 (m, 7 H, 3×PhCH2 and H-1), 4.07 (dd,
1 H, J 9.70, 7.70 Hz, H-2), 3.74–3.79 (m, 2 H), 3.73 (s,
3 H, OCH3), 3.57 (m, 1 H, H-6b), 3.42–3.49 (m, 2 H);
13C NMR (100 MHz, CDCl3): 151.2, 151.4 (C-1 and
C-4, Mp), 138.5, 138.3, 138.2, 128.6, 128.5, 128.3, 128.2,
128.0, 127.8, 127.6 (Ar-C), 118.3 (2 C, Mp), 114.5 (2 C,
Mp), 102.9 (C-1), 82.2, 79.3, 75.4, 74.9, 74.2, 73.4, 72.7
(C-2,3,4,5 and OCH2Ph), 61.9 (C-6), 55.7 (OCH3).
Anal. Calcd for C34H36O7: C, 73.40; H, 6.47. Found: C,
73.15; H, 6.49.
It has been reported that the glycosidic bond of
fucose is very sensitive under acidic conditions.15 To
enhance its tolerance to acidic treatment and simplify
the final deprotection steps, the electron-donating ben-
zyl groups were replaced by electron-withdrawing acetyl
groups in the following steps (Scheme 4). The first
attempt to hydrogenate 11 by using 20% Pd(OH)2–C as
a catalyst failed since a considerable amount of deiso-
propylidenation product was formed, along with the
desired compound. However, 20% Pd–C was a suitable
alternative which effectively suppressed this side reac-
tion. After acetylation and deisopropylidenation with
TsOH·H2O, the 4%%-OH of the non-reducing terminal
galactose was selectively protected with an acetyl group
by using the trimethyl orthoacetate method.16 Sulfation
of 15 with the SO3·Py complex in DMF followed by
deacetylation with methanolic sodium methoxide and
then passing through Sephadex G-10 resin gave the
target compound 17 as an amorphous sodium salt.
In conclusion, we have synthesized a sulfated tetra-
saccharide having potential E-selectin-binding activities
in a highly practical way. The biological investigations
of the target compound may expand the library of
biological tools and provide useful information for SAR
research of Lewis sugar-based selectin antagonists.

624
Z.-H. Qin et al. / Carbohydrate Research 337 (2002) 621–628
If the crude product was not treated with NaOMe, a
OMp), 3.60–5.06 (m, 13 H), 3.77 (s, 3 H, OCH3), 1.98
(s, 3 H, CH3CO).
4-Methoxyphenyl (3,4-O-isopropylidene-i-
pyranosyl)-(1“4)-(i- -glucopyranosyl)-(1“6)-2,3,4-
tri-O-benzyl-i- -galactopyranoside (8).—Compound 6
noticeable amount of formylated product 5 could be
separated by column chromatography as white needles,
mp 113–114 °C, [h]D −10.1° (c 1.19, CH2Cl2); Rf 0.48
(1:3 acetone–light petroleum); 1H NMR (300 MHz,
CDCl3): 7.91 (s, 1 H, HCOO), 7.28–7.36 (m, 15 H,
Ar-H), 6.78–7.01 (AA%BB%, 4 H, Mp), 4.65–5.04 (m, 7
H, 3×PhCH2 and H-1), 4.30–4.36 (m, 1 H, H-6a),
4.07–4.1 (m, 2 H), 3.81–3.85 (m, 1 H), 3.76 (s, 3 H,
OCH3), 3.58–3.66 (m, 2 H); 13C NMR (75 MHz,
CDCl3) 160.4 (HCOO), 155.3, 151.5 (C-1 and C-4,
Mp), 138.4, 138.2, 138.0, 128.5, 128.4, 128.2, 127.8,
127.7, 127.6 (Ar-C), 118.6 (2 C, Mp), 114.5 (2 C, Mp),
103.2 (C-1), 82.0, 79.1, 75.4, 74.4, 73.5, 72.8, 72.2
(C-2,3,4,5 and PhCH2), 62.7 (C-6), 55.6 (OCH3). Anal.
Calcd for C35H36O8: C, 71.93; H, 6.16. Found: C, 71.79;
H, 6.25.
D
-galacto-
D
D
(4.0 g, 3.4 mmol) was dissolved in MeOH (30 mL), and
1 M NaOMe–MeOH (3 mL) was added dropwise. The
mixture was stirred overnight at rt. After neutralization
with cationic resin (H+), the solution was concentrated
and toluene evaporated from the residue. 2,2-
Dimethoxypropane (40 mL) and CSA (30 mg) were
added to the residue and the mixture was stirred for 24
h at rt. The clear solution so obtained was neutralized
with a few drops of Et3N and concentrated. Methanol
(40 mL) and water (4 mL) were added to the residue
and the mixture was refluxed for 6 h. The solution was
concentrated, toluene evaporated from it, and the
residue was purified by column chromatography to
afford the title compound as white foam (2.2 g, 71%),
mp 102–104 °C, [h]D −40.91° (c 0.88, CH2Cl2); Rf 0.21
(1:1 CHCl3–MeOH); 1H NMR (300 MHz, CDCl3):
7.20–7.28 (m, 15 H, ArH), 6.82 (AA%BB%, 4 H, Mp),
3.15–4.88 (m, 30 H), 1.38 (s, 3 H, CMe2),1.20 (s, 3 H,
CMe2); 13C NMR (75 MHz, CDCl3): 154.8, 151.3 (C-1
and C-4, Mp), 138.3, 138.3, 128.3, 128.2, 128.1, 127.5,
127.3 (Ar-C), 118.1, 114.5 (2 C each, OMp), 110.2
[(CH3)2C], 102.7, 102.3, 102.2 (C-1, C-1%, C-1%%), 81.8,
80.3, 79.2, 79.0, 76.6, 75.2, 74.9, 74.3, 74.0, 73.7, 73.2,
73.0, 68.5, 61.8, 61.4 (sugar C and PhCH2), 55.5
(OCH3), 26.9, 26.1 [(CH3)2C]; MALDI-TOF: 943.6
[M+Na]+, 960.1 [M+K]+. Anal. Calcd for
C49H60O17: C, 63.93; H, 6.51. Found: C, 63.68; H, 6.48.
4-Methoxyphenyl (2,6-di-O-benzoyl-3,4-O-isopropyli-
4-Methoxyphenyl
actopyranosyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
pyranosyl)-(1“6)-2,3,4-tri-O-benzyl-i- -galactopyra-
noside (6) and 4-methoxyphenyl 6-O-acetyl-2,3,4-tri-O-
benzyl-i- -galactopyranoside (7).—Compound 5 (3.0
(2,3,4,6-tetra-O-acetyl-i-
D-gal-
D
-gluco-
D
D
g, 5.42 mmol) was dissolved in CH2Cl2 (50 mL), and
powdered molecular sieve (3.5 g) was added. After
being stirred at rt for 3 h, the mixture was cooled to
0 °C and Ag2CO3 (6.0 g), and AgOTf (3.5 g) were
added successively. The peracetylated lactosyl bromide
(10.0 g) dissolved in CH2Cl2 (25mL) was then added
dropwise. the mixture was kept at 0 °C for 2 h and
stirred overnight at rt. After dilution with CH2Cl2 and
filtration through Celite, the filtrate was washed succes-
sively with satd NaHCO3, 10% Na2S2O3, water, and
satd NaCl. The solution was dried, concentrated, and
the residue purified with column chromatography (1:1
light petroleum–EtOAc) to afford the title compound 6
as a white foam (5.3 g, 83%), mp 88–90 °C, [h]D
−9.64° (c 0.83, CH2Cl2); Rf 0.26 (1:1 light petroleum–
dene-i-
i- -glucopyranosyl)-(1“6)-2,3,4-tri-O-benzyl-i-
galactopyranoside (9) and 4-methoxyphenyl (2,6-di-O-
benzoyl-3,4-O-isopropylidene-i- -galactopyranosyl)-
(1“4)-(2,3,6-tri-O-benzoyl-i- -glucopyranosyl)-(1“6)-
2,3,4-tri-O-benzyl-i- -galactopyranoside (10).—Com-
D
-galactopyranosyl)-(1“4)-(2,6-di-O-benzoyl-
D
D-
D
1
EtOAc); H NMR (400 MHz, CDCl3): 7.26–7.37 (m,
D
15 H, ArH), 6.95 (AA%BB%, 4 H, OMp), 3.58–5.34 (30
H, m, sugar H, 3×PhCH2, OCH3), 2.14 (s, 3 H, OAc),
2.05 (s, 6 H, 2×OAc), 2.04 (s, 6 H, 2×OAc), 1.96 (s,
3 H, OAc), 1.89 (s, 3 H, OAc); 13C NMR (75 MHz,
CDCl3): 170.2, 170.0, 169.5, 169.0 (CꢀO), 155.2, 151.5
(C-1 and C-4, Mp), 138.4, 138.2, 138.2, 128.4, 128.3,
128.3, 128.2, 128.2, 127.7, 127.7, 127.6, 127.5 (Ar-C),
117.9, 114.6 (2 C each, Mp), 102.8 (C-1), 100.9, 100.1
(C-1%, C-1%%), 81.7, 79.1, 76.1, 75.3, 74.9, 74.3, 73.4, 73.2,
72.7, 72.4, 71.8, 70.9, 70.6, 69.0, 68.7, 66.5, 61.9, 60.7
(sugar C and PhCH2), 55.6 (OCH3), 20.7, 20.6, 20.5,
20.5, 20.4, 20.4 (CH3CO); MALDI-TOF: 1197.4 [M+
Na]+, 1213.4 [M+K]+. Anal. Calcd for C60H70O24: C,
61.30; H, 6.01. Found: C, 60.95; H, 5.88.
D
pound 8 (600 mg, 0.65 mmol) was dissolved in toluene
(6 mL) and pyridine (4.5 mL), and then cooled to 0 °C,
and benzoyl chloride (600 mL) was added dropwise. The
mixture was stirred at 0 °C for 3 h, and MeOH (1 mL)
was added to quench the reaction. After dilution with
EtOAc (50 mL), the solution was successively washed
with cold 1 M H2SO4, satd NaHCO3, and water, dried
with MgsO4 and then concentrated. The residue was
purified by column chromatography to afford com-
pound 9 as white foam (570 mg, 65.4%), mp 96–98 °C,
[h]D +15.69° (c 0.51, CH2Cl2); Rf 0.40 (2.5:1 cyclohex-
ane–EtOAc); IR: 3460 cm−1 (ꢁOH); 1H NMR (400
MHz, CDCl3): 7.15–8.04 (m, 35 H, ArH), 6.86
(AA%BB%, 4 H, OMp), 5.35 (t, 1 H, J 7.80 Hz, H-2%),
5.18 (dd, 1 H, H-2%%), 4.93, 4.91, 4.75, 4.70 (ABq, 2 H,
PhCH2), 4.79 (dd, 1 H, H-5%), 4.80, 4.75, 4.58, 4.56
(ABq, 2 H, PhCH2), 4.60–4.68 (m, 3 H, H-1, H-1%,
The acetylated glycosyl acceptor 7 was also separated
as byproduct, Rf 0.62 (1:1 light petroleum–EtOAc),
1
[h]D −8.51° (c 0.94, CH2Cl2); H NMR (300 MHz,
CDCl3): 7.24–7.39 (m, 15 H, ArH), 6.92 (AA%BB%, 4 H,

Z.-H. Qin et al. / Carbohydrate Research 337 (2002) 621–628
625
H-1%%), 4.42–4.49 (ABq, 2 H, PhCH2), 4.37–4.40 (m, 2
H, H-6%), 4.26–4.27 (m, 3 H, H-3, H-4, H-6a%%), 4.00–
4.25 (m, 1 H, H-6b%%), 3.89–3.94 (m, 2 H, H-2, H-3%%),
3.76 (s, 3 H, OCH3), 3.71–3.75 (m, 4 H, H-4, H-4%%,
H-6), 3.57–3.58 (m, 1 H, H-5%%), 3.41–3.43 (m, 1 H,
H-5%), 3.35 (dd, 1 H, J3,4 2.89, J2,3 9.78 Hz, H-3), 1.63,
1.35 [2 s, 6 H, C(CH3)2]; 13C NMR (100 MHz, CDCl3):
166.5, 165.5, 165.3, 165.2 (PhCO), 155.3, 151.5 (C-1
and C-4, Mp), 138.3, 133.1, 129.9, 129.8, 129.8, 129.7,
129.6, 129.6, 129.1, 128.8, 128.4, 128.4, 128.4, 128.3,
128.3, 128.2, 128.2, 128.1, 127.6, 127.5, 127.5, 127.4
(Ar-C), 118.9, 114.5 (2 C each, Mp), 111.2 [(CH3)2C],
103.3 (C-1), 101.5 (C-1%), 100.5 (C-1%%), 82.2 (C-4%%), 81.9
(C-3), 78.9 (C-2), 75.3 (PhCH2), 74.5 (PhCH2), 74.1(C-
5), 73.4 (C-3%%), 73.4 (C-4), 73.2 (C-3%), 73.0 (C-2%), 73.0
(C-2%%), 72.8 (PhCH2), 72.1 (C-4%, C-5%%), 67.8 (C-6), 63.7
(C-6%, C-5%), 62.4 (C-6%%), 55.6 (OCH3), 27.6, 26.3
[(CH3)2C]; MALDI-TOF: 1358.9 [M+Na]+, 1375.4
[M+K]+. Anal. Calcd for C77H76O21: C, 69.15; H,
5.73. Found: C, 68.89; H, 5.91.
stirred continuously for 30 h, and then diluted with
CH2Cl2.The precipitate was filtered off and the filtrate
was successively washed with satd NaHCO3, water, and
satd NaCl solution, dried with MgSO4 and then con-
centrated. The crude product was purified by column
chromatography (2:3:1.5 cyclohexane–toluene–EtOAc)
to afford 11 as a white foam (1.3 g, 70.8%), mp
94–96 °C, [h]D +25.6° (c 1.25, CH2Cl2); Rf 0.60
1
(2:3:1.5 cyclohexane–toluene–EtOAc), H NMR (400
MHz, CDCl3): 6.79–8.13 (m, 54 H, Ar-H), 5.38–5.41
(m, 2 H, H-2%, Fuc H-1), 5.23 (t, 1 H, H-2%%), 4.88–4.94
(m, 3 H, PhCH2, Fuc H-5), 4.73–4.79 (m, 5 H, 2×
PhCH2, H-6a%%), 4.55–4.64 (m, 3 H, H-1 and PhCH2),
4.43–4.49 (m, 6 H, H-1%, H-1%%, H-6%and PhCH2), 4.24–
4.32 (m, 2 H, H-4 and H-6b%%), 4.12–4.22 (m, 5 H, H-3,
H-3%, H-3%%, PhCH2), 4.08 (t, 1 H, H-4%), 3.88–3.91 (m,
2 H, H-2, Fuc H-2), 3.73–3.79 (m, 4 H, H-4, H-5%%,
H-6b, Fuc H-4), 3.72 (s, 3 H, OCH3), 3.60–3.64 (m, 1
H, H-6a), 3.30–3.32 (m, 1 H, H-5%), 3.27–3.30 (m, 2 H,
H-5, Fuc H-3), 1.50, 1.30 [2 s, 6 H, C(CH3)2], 1.32 (d,
3 H, Fuc H-6); 13C NMR (100M Hz, CDCl3): 166.1,
165.9, 164.7 (PhCO), 155.4, 151.4 (C-1 and C-4, Mp),
139.1, 138.7, 138.4, 138.3, 138.3, 138.1, 137.8, 133.5,
133.4, 133.4, 129.8, 129.7, 129.6, 129.5, 129.4, 129.3,
129.2, 129.1, 128.9, 128.7, 128.6, 128.6, 128.5, 128.2,
128.2, 128.2, 128.1, 128.1, 128.0, 128.0, 127.7, 127.5,
127.4, 127.4, 127.4, 127.3, 126.9, 126.7, 125.2 (Ar-C),
118.9, 114.4 (2 C each, Mp), 110.8 [(CH3)2C], 103.2
(C-1), 101.0, 100.1 (C-1%, C-1%%), 97.4 (Fuc C-1), 81.7
(Fuc C-3), 79.1 (C-3%%), 78.8 (C-2), 78.2 (C-4), 77.2
(C-3%), 75.5 (Fuc C-2), 75.2 (PhCH2), 74.9 (PhCH2),
74.8 (C-2%), 74.7 (C-4%), 74.4 (PhCH2), 73.9 (C-3), 73.6
(C-5), 73.3 (PhCH2), 73.2 (C-5%), 73.1 (C-2%%), 73.0 (Fuc
C-4), 72.6 (PhCH2), 72.5 (C-4%%and PhCH2), 71.4 (C-
5%%), 67.4 (C-6), 66.4 (Fuc C-5), 62.6 (C-6%%), 62.2 (C-6%),
55.7 (OCH3), 27.7, 26.2 [(CH3)2C], 16.8 (Fuc C-6);
MALDI-TOF: 1775.2 [M+Na]+, 1790.9 [M+K]+.
Anal. Calcd for C104H104O25: C, 71.22; H, 5.98. Found:
C, 71.20; H, 5.94.
The perbenzoylated product (10, 110 mg) was also
obtained as a colorless syrup, [h]D +25.23° (c 1.11,
1
CH2Cl2); Rf 0.48 (2.5:1 cyclohexane–EtOAc); H NMR
(400 MHz, CDCl3): 7.17–8.08 (m, 40 H, ArH), 6.96
(AA%BB%, 4 H, Mp), 5.65 (t, 1 H, J 9.48 Hz, H-3%), 5.38
(dd, 1 H, J 7.99, 9.58 Hz, H-2%), 5.12 (t, 1 H, J 7.19 Hz,
H-2%%), 4.53–4.96 (m, 10 H, 3×PhCH2, H-1, H-1%,
H-1%%, H-6a%), 4.44–4.50 (m, 1 H, H-6b%), 4.18–4.23 (m,
3 H, H-3%%, H-4%, H-6a), 4.04–4.06 (m, 1 H, H-6b),
3.94–3.96 (m, 1 H, H-2), 3.80 (s, 3 H, OCH3), 3.64–
3.79 (m, 6 H, H-4, H-5, H-4%%, H-5%%, H-6a%%, H-5%),
3.390–3.393 (m, 1 H, H-6b%%), 3.38–3.39 (dd, 1 H, H-3),
1.51, 1.24 (2s, 6 H, CMe2); 13C NMR (100 MHz,
CDCl3): 165.9, 165.8, 165.4, 165.2, 164.9 (PhCO),
155.5, 151.3 (Mp), 138.4, 138.3, 138.2, 133.4, 133.2,
132.9, 129.9, 129.8, 129.8, 129.7, 129.6, 129.5, 129.5,
129.3, 129.2, 128.7, 128.5, 128.4, 128.3, 128.3, 128.2,
128.1, 128.1, 127.6, 127.5, 127.4 (Ar-C), 118.7, 114.6 (2
C each, Mp), 110.8 [(CH3)2C], 103.0 (C-1), 100.5, 100.1
(C-1%, C-1%%), 81.8, 78.9, 75.3, 75.2, 74.4, 74.4, 73.5, 73.3,
73.1, 72.9, 72.9, 72.6, 72.0, 71.3, 67.9, 62.8, 62.4 (sugar
C and PhCH2), 55.7 (OCH3), 27.4, 26.9 [(CH3)2C].
Anal. Calcd for C84H80O22: C, 69.99; H, 5.59. Found:
C, 69.64; H, 5.45.
(2,3,4-Tri-O-benzyl-a-
L-fucopyranosyl) 2,3,4-tri-O-
benzyl-b- -fucopyranoside (12, 190 mg) was also sepa-
L
rated as a colorless syrup, [h]D −24.78° (c 1.36,
CH2Cl2); Rf 0.75 (2:3:1.5 toluene–cyclohexane–
1
EtOAc); H NMR (400 MHz, CDCl3): 7.16–7.31 (m,
30 H, ArH), 5.20 (d, 1 H, J1,2 3.31 Hz, Fuc a H-1),
4.60–5.08 (m, 12 H, 6×PhCH2), 4.50 (d, 1 H, J1,2 7.83
Hz, Fuc b H-1), 4.30 (m, 1 H, Fuc a H-5), 4.02–4.11
(m, 2 H, Fuc a H-2, Fuc a H-4), 3.82–3.86 (m, 1 H,
Fuc b H-2), 3.65 (br, 1 H, Fuc a H-3), 3.44–3.51 (m, 3
H, Fuc b H-3, b H-4, b H-5), 1.05–1.10 (m, 6 H, Fuc
a H-6, Fuc b H-6); 13C NMR (100 MHz, CDCl3):
139.0, 138.8, 138.7, 138.5, 138.5, 138.4, 128.5, 128.2,
128.1, 128.1, 128.0, 127.9, 127.6, 127.5, 127.5, 127.4,
127.4, 127.3, 127.3, 127.2, 127.0 (Ar-C), 103.6 (Fuc b
C-1), 99.8 (Fuc a C-1), 82.6, 78.6, 77.9, 76.0, 75.9, 74.7,
74.4, 73.2, 73.0, 72.6, 70.5, 67.1 (sugar C and PhCH2),
16.8 (Fuc C-6), 16.2 (Fuc C-6).
4-Methoxyphenyl (2,6-di-O-benzoyl-3,4-O-isopropyli-
dene-i-
benzyl-h-
-glucopyranosyl)-(1“6)-2,3,4-tri-O-benzyl-i-
actopyranoside (11).—Compound 9 (1.3 g, 1 mmol),
-fucopyranoside (1.8
D
-galactopyranosyl)-(1“4)-O-[(2,3,4-tri-O-
-fucopyranosyl)-(1“3)-2,6-di-O-benzoyl-i-
-gal-
L
D
D
ethyl 2,3,4-tri-O-benzyl-1-thio-b-
L
g, 3.8 mmol), and 2,6-di-t-butyl-4-methylpyridine (205
mg) were dissolved in 1,2-dichloroethane (20 mL) and
,
DMF (4 mL), powdered 4 A molecular sieves (2.5 g)
were added, and the mixture was stirred at rt for 5 h.
Tetrabutylammonia bromide (1.9 g, 6 mmol), and
CuBr2 (1.3 g, 6 mmol) were added, and the mixture was

626
Z.-H. Qin et al. / Carbohydrate Research 337 (2002) 621–628
4-Methoxyphenyl (2,6-di-O-benzoyl-3,4-O-isopropyli-
dene-i- -galactopyranosyl)-(1“4)-[(2,3,4-tri-O-acetyl-
-fucopyranosyl)-(1“3)-2,6-di-O-benzoyl-i- -gluco-
pyranosyl]-(1“6)-2,3,4-tri-O-acetyl-i- -galactopyra-
OMp), 5.37–5.38 (m, 1 H, Fuc H-4), 5.25–5.33 (m, 5
D
H, Fuc H-3, H-2, H-4, H-2%, H-2%%), 5.24 (d, 1 H, J1,2
4.04 Hz, Fuc H-1), 5.10–5.22 (m, 1 H, Fuc H-5), 5.03
(dd, 1 H, J1,2 3.97, J2,3 10.80 Hz, Fuc H-2), 4.94 (dd, 1
H, J3,4 3.47, J2,3 10.45 Hz, H-3), 4.86 (m, 1 H, H-6a%%),
4.64–4.73 (m, 4 H, H-1, H-1%%, H-6a%, H-6b%%), 4.55 (d, 1
H, J1,2 8.01 Hz, H-1%), 4.43 (m, 1 H, H-6b%), 4.07–4.14
(m, 2 H, H-3%, H-4%), 3.97–3.98 (m, 1 H, H-4%%), 3.76 (s,
3 H, OCH3), 3.65–3.74 (s, 5 H, H-5, H-6, H-3%%, H-5%%),
3.59–3.61 (m, 1 H, H-5%), 2.04, 2.03, 1.97, 1.92, 1.89,
1.88 (6 s, 18 H, 6×CH3CO), 1.28 (d, 3 H, J5,6 6.54 Hz,
Fuc H-6); 13C NMR (100 MHz, CDCl3): 170.7, 170.4,
170.0, 169.8, 169.3, 166.4, 165.9, 165.8, 164.7 (PhCO
and CH3CO), 155.8, 151.0 (C-1 and C-4, Mp), 133.4,
133.4, 129.9, 129.8, 129.8, 129.6, 129.4, 129.3, 129.3,
129.0, 128.7, 128.6, 128.6, 128.5 (Ar-C), 118.8, 114.6 (2
C each, Mp), 100.9 (C-1%%), 100.6 (C-1), 100.1 (C-1%),
96.2 (Fuc C-1), 74.8 (C-3%), 74.1, 73.4, 73.3 (C-5%), 73.3
(C-4%), 73.2 (C-5%%), 72.6, 72.5, 71.5 (Fuc C-4), 70.6
(C-3), 68.8, 68.7, 68.1 (C-4%%), 67.6, 67.0 (Fuc C-2), 66.6
(C-6), 64.7 (Fuc C-5), 62.1 (C-6%), 62.0 (C-6%%), 55.6
(OCH3), 20.68, 20.65, 20.54, 20.47, 20.45, 20.37 (6×
CH3CO), 15.7 (Fuc C-6); MALDI-TOF: 1448.2 [M+
Na]+, 1464.1 [M+K]+; Anal. Calcd for C71H76O31: C,
59.83; H, 5.37. Found: C, 59.95; H, 5.10.
L
D
D
noside (13).—A solution of 11 (600 mg, 0.34 mmol) in
MeOH (40 mL) and 1,4-dioxane (40 mL) was stirred
for 12 h at rt in the presence of a catalytic amount of
20% Pd–C under hydrogen, then filtered, and concen-
trated. A solution of the residue in pyridine (15 mL)
and Ac2O (10 mL) was stirred for 24 h at rt, and then
cooled in an ice bath. Methanol (10 mL) was added and
after stirring for 0.5 h, the mixture was concentrated
and coevaporated with benzene twice to afford the title
compound. The crude product (360 mg, 71.8%) was
used in the next step without further purification.
Preparative TLC was performed to obtain a sample for
NMR analysis. [h]D −45.3° (c 0.5, CH2Cl2); Rf 0.31
(2:1 cyclohexane–acetone); 1H NMR (400 MHz,
CDCl3): 7.27–8.11 (m, 20 H, ArH), 6.78–6.83 (AA%BB%,
4 H, Mp), 5.25–5.40 (m, 7 H, H-2, H-4, H-2%, H-2%%,
Fuc H-1, Fuc H-3, Fuc H-4), 5.14–5.16 (m, 1 H, Fuc
H-5), 5.02–5.10 (m, 1 H, Fuc H-2), 4.90–4.94 (m, 2 H,
H-3, H-6a%%), 4.81 (m, 1 H, H-6b%%), 4.69 ( d, 1 H, J1,2
7.97 Hz, H-1), 4.63–4.66 (m, 1 H, H-6a%), 4.53–4.55
(m, 2 H, H-1%, H-1%%), 4.42 (m, 1 H, H-6b%), 4.25–4.28
(m, 1 H, H-3%%), 4.17–4.19 (m, 1 H, H-4%%), 4.07–4.12
(m, 2 H, H-3%, H-4%), 3.80–4.02 (m, 1 H, H-5%%), 4.77 (s,
3 H, OCH3), 3.64–3.73 (m, 3 H, H-5, H-6), 3.45 (m, 1
H, H-5%), 2.11, 2.04, 1.96, 1.92, 1.86. 1.85 (6 s, 6×
OAc), 1.60, 1.33 [2 s, 6 H, C(CH3)2], 1.34 (d, 3 H, J
4.94 Hz, Fuc H-6); 13C NMR (100 MHz, CDCl3):
170.5, 170.0, 169.8, 169.5, 169.3, 166.2, 165.8, 164.8,
164.7 (PhCO, CH3CO), 155.8, 151.0 (Mp), 133.5,
133.4, 133.3, 130.3, 129.7, 129.6, 129.3, 129.2, 129.1,
129.0, 128.7, 128.6, 128.6, 128.5 (Ar-C), 118.8, 114.6 (2
C each, Mp), 111.0 [(CH3)2C], 100.9, 100.4, 100.3 (C-1,
C-1%, C-1%%), 96.3 (Fuc C-1), 77.4 (C-3%), 74.9, 74.2 (C-3),
74.2, 73.4 (C-4), 73.2 (C-4%, C-5%%), 72.1 (C-5), 71.6
(C-5%), 70.6 (C-2), 68.8 (C-3%%), 68.2 (Fuc C-3), 67.6, 67.0
(Fuc C-2), 66.7 (C-6%%), 64.6 (Fuc C-5), 62.7 (C-6%), 61.9
(C-6), 55.7 (OCH3), 27.7, 26.0 [(CH3)2C], 20.7, 20.6,
20.5, 20.5, 20.5, 20.4 (6×CH3CO), 16.0 (Fuc C-6).
4-Methoxyphenyl (4-O-acetyl-2,6-di-O-benzoyl-i-
galactopyranosyl)-(1“4)-O-[(2,3,4-tri-O-acety-h-
D
-
-
L
fucopyranosyl) - (1“3) - 2,6 - di - O - benzoyl - i -
D - gluco-
pyranosyl]-(1“6)-2,3,4-tri-O-acetyl-i- -galactopyra-
D
noside (15).—Compound 14 (400 mg) was dissolved in
benzene (3 mL), and trimethyl orthoacetate (750 mL)
and CSA (10 mg) were added to the solution. The
mixture was stirred at rt for 0.5 h and then two drops
of Et3N added. After concentration, 80% HOAc (2.5
mL) was added to the residue and the solution was
stirred at rt for 20 min. The mixture was diluted with
CH2Cl2 (50 mL) and washed with satd NaHCO3. The
aqueous phase was back extracted with CH2Cl2 and the
combined organic layer was dried with MgSO4 and
then concentrated. Preparative TLC (1:2 acetone–cy-
clohexane) of the residue gave the title compound as a
white foam (370 mg, 90%), mp 156–158 °C. [h]D
−49.23° (c 0.65, CH2Cl2); Rf 0.35 (2:1 cyclohexane–
4-Methoxyphenyl (2,6-di-O-benzoyl-i-
ranosyl)-(1“4)-[(2,3,4-tri-O-acetyl-h- -fucopyranosyl)-
(1“3)-2,6-di-O-benzoyl-i- -glucopyranosyl]-(1“6)-
2,3,4-tri-O-acetyl-i- -galactopyranoside (14).—Com-
D-galactopy-
1
L
acetone); H NMR (400 MHz, CDCl3): 7.27–8.12 (m,
D
20 H, ArH), 6.78–6.86 (AA%BB%, 4 H, Mp), 5.46–5.47
(m, 1 H, Fuc H-4), 5.39–5.40 (m, 1 H, H-4%%), 5.24–5.33
(m, 6 H, H-2, H-4, Fuc H-1, Fuc H-3, H-2%, H-2%%), 5.18
(m, 1 H, Fuc H-5), 5.05 (dd, 1 H, J1,2 3.94, J2,3 10.90
Hz, Fuc H-2), 4.94 (dd, 1 H, J3,4 3.38, J2,3 10.48 Hz,
H-3), 4.68–4.75 (m, 5 H, H-1, H-1%%, H-6%%, H-6a%), 4.57
(d, 1 H, J1,2 9.81 Hz, H-1%), 4.42–4.46 (m, 1 H, H-6b%),
4.09–4.12 (m, 2 H, H-3%, H-4%), 3.93 (dd, 1 H, J3,4 3.58,
J2,3 9.81 Hz, H-3%%), 3.76 (s, 3 H, OCH3), 3.65–3.75 (m,
4 H, H-5, H-6, H-5%%), 3.48 (br, 1 H, H-5%), 2.22, 2.11,
2.10, 2.04, 1.96, 1.91, 1.87 (7 s, 21 H, 7×CH3CO), 1.36
(d, 3 H, J5,6 6.51 Hz, Fuc H-6); 13C NMR (100 MHz,
D
pound 13 (650 mg) was dissolved in MeOH (3 mL) and
EtOAc (3 mL), and TsOH·H2O (90 mg) was added.
The mixture was stirred at rt for 2.5 h. After neutraliza-
tion with a few drops of Et3N, the solution was concen-
trated and the crude product purified by preparative
TLC (2:1 cyclohexane–acetone) to afford the title com-
pound as a white foam (450 mg, 69.2%), mp 152–
154 °C, [h]D −40.91° (c 0.88, CH2Cl2); Rf 0.21 (1:2
acetone–cyclohexane); 1H NMR (400 MHz, CDCl3):
7.26–8.14 (m, 20 H, ArH), 6.77–6.86 (AA%BB%, 4 H,

Z.-H. Qin et al. / Carbohydrate Research 337 (2002) 621–628
627
CDCl3): 171.1, 170.6, 169.9, 169.8, 169.3, 165.9, 165.8,
165.3, 164.6 (PhCO and CH3CO), 155.7, 150.9 (C-1
and C-4, Mp), 133.5, 133.4, 133.3, 129.8, 129.7, 129.5,
129.2, 129.0, 128.9, 128.9, 128.7, 128.6, 128.5, 128.4
(Ar-C), 118.7, 114.5 (2 C each, Mp), 100.8 (C-1%%), 100.5
(C-1), 100.4 (C-1%), 96.2 (Fuc C-1), 74.6 (C-3%), 74.0,
73.8 (C-4%),73.2 (C-5%), 73.1, 72.5, 71.7, 71.3 (Fuc C-4),
71.1 (C-3%%), 70.5 (C-3), 69.3 (C-4%%), 68.7, 68.4 (C-2%%),
67.5, 66.7 (Fuc C-2), 66.6 (C-6), 64.3 (Fuc C-5), 61.9
(C-6%), 61.3 (C-6%%), 55.6 (OCH3), 20.6, 20.6, 20.5, 20.4,
20.4, 20.4, 20.3 (7×CH3CO), 15.8 (Fuc C-6). MALDI-
TOF: 1489.2 [M+Na]+, 1505.3 [M+K]+. Anal.
Calcd for C73H78O32: C, 59.75; H, 5.36. Found: C,
59.47; H, 5.19.
removed below 40 °C in a vacuum. The residue was
dissolved in water (2 mL) and then purified by column
chromatography on Sephadex G-10. After lyophiliza-
tion, the title compound was obtained as a white amor-
phous solid mass (20 mg, 64.5%), [h]D −72.7° (c 0.11,
1
water); H NMR (400 MHz, D2O): 5.45 (d, 1 H, J1,2
4.00 Hz, Fuc H-1), 5.00 (d, 1 H, J1,2 7.20 Hz, H-1),
4.49–4.54 (m, 2 H, H-1%, H-1%%), 4.32 (dd, 1 H, J3,4 3.20,
J2,3 10.00 Hz, H-3%%), 4.07–4.27 (m, 1 H, Fuc H-3),
4.02–4.07 (m, 3 H, H-4, H-6a, H-6a%%), 3.95–3.99 (m, 3
H, Fuc H-3, H-5, H-6b%%), 3.88 (t, 1 H, J 9.20 Hz, H-4%),
3.83 (s, 3 H, OCH3), 3.71–3.81 (m, 8 H, Fuc H-2, H-2%,
H-3%, H-6%, H-5%%, H-2, H-6b, H-4), 3.62–3.65 (m, 2 H,
H-2%%, H-4%%), 3.54 (t, 3 H, J 8.00 Hz, H-2%), 3.42–3.46
(m, 1 H, H-5%), 1.19 (d, 3 H, J5,6 6.80 Hz, Fuc H-6); 13C
NMR (100 MHz, D2O): 155.5, 151.7 (C-1 and C-4,
Mp), 119.0 (2 C, Mp), 115.9 (2 C, Mp), 103.1 (C-1%),
102.3 (C-1%%), 102.2 (C-1), 99.2 (Fuc C-1), 81.0 (C-3%%),
77.7, 76.0 (C-5%%), 75.5 (2 C, C-2, C-4%%), 75.0 (C-4), 73.7,
73.3, 72.8, 71.4, 70.1 (C-2%%), 69.7 (C-6%%), 69.6, 68.9
(C-4%), 67.5 (Fuc C-3), 67.3 (Fuc C-5), 62.2 (C-6%), 60.5
(C-6), 56.8 (OCH3), 16.1 (Fuc C-6); MALDI-TOF:
834.2 [M−Na]+.
4-Methoxyphenyl (4-O-acetyl-2,6-di-O-benzoyl-3-O-
sulfo-i-
h- -fucopyranosyl)-(1“3)-2,6-di-O-benzoyl-i-
pyranosyl]-(1“6)-2,3,4-tri-O-acetyl-i- -galactopyra-
D
-galactopyranosyl)-(1“4)-[(2,3,4-tri-O-acety-
L
D
-gluco-
D
noside triethylammonium salt (16).—A mixture of (60
mg, 0.041 mmol) and pyridine–sulfur trioxide complex
(40 mg) in DMF (0.5 mL) was stirred at rt for 3 h. A
few drops of Et3N were added and the solvent was
removed below 40 °C in a vacuum. The residue was
purified by preparative TLC to afford the title com-
pound as an amorphous solid mass (70 mg, quantitative
Acknowledgements
1
yield), [h]D −43.2° (c 0.37, CH2Cl2); H NMR (400
MHz, CDCl3): 5.81 (br, 1 H, H-3%%), 5.44 (br, 1 H, Fuc
H-4), 5.25–5.33 (m, 6 H, Fuc H-1, H-3, H-2, H-4,
H-2%%, H-4%%), 5.20–5.21 (m, 1 H, Fuc H-5), 5.04 (dd, 1
H, J1,2 3.76, J2,3 10.86 Hz, Fuc H-2), 4.96 (dd, 1 H, J3,4
3.26, J2,3 10.22 Hz, H-3), 4.69–4.85 (m, 6 H, H-1, H-1%%,
H- 2%%, H-6%%, H-6a%), 4.53 (d, 1 H, J 7.95 Hz, H-1%),
4.21–4.24 (m, 1 H, H-6b%), 4.00–4.14 (m, 3 H, H-3,
H-4%, H-5%%), 3.76 (s, 3 H, OCH3), 3.57–3.69 (m, 3 H,
H-5, H-6), 3.41–3.43 (br, 1 H, H-5%), 2.83–2.94 [q, J
7.43 Hz, (CH3CH2)3N], 2.11 (s, 6 H, 2×CH3CO), 2.05
(s, 3 H, CH3CO), 1.92 (s, 6 H, 2×CH3CO), 1.86 (s, 3
H, CH3CO), 1.82 (s, 3 H, CH3CO), 1.35 (d, 3 H, J5,6
6.25 Hz, Fuc H-6), 1.11 [t, J 7.29 Hz, (CH3CH2)3N];
13C NMR (100 MHz, CDCl3): 170.6, 169.9, 169.8,
169.78, 169.73, 169.32, 166.0, 165.5, 164.7 (PhCO,
CH3CO), 155.8, 151.0 (C-1 and C-4, Mp), 114.6 (2 C,
Mp), 100.83 (C-1%%), 100.8 (C-1), 100.39 (C-1%), 96.2
(Fuc C-1), 75.1, 74.6, 74.0, 73.5, 73.2, 71.8, 71.4, 70.6,
70.1, 68.9, 68.6, 67.6, 66.8, 66.6, 64.4, 61.6, 60.3 (sugar
C), 55.6 (OCH3), 46.3 [CH3CH2]3N], 20.8, 20.7, 20.6,
20.5, 20.5, 20.4, 20.3 (7×CH3CO), 15.8 (Fuc C-6), 8.4
[(CH3CH2)3N]; MALDI-TOF: 1544.0 [M−NH-
(C2H5)3]+.
This project was supported by the National Natural
Science Foundation of the People’s Republic of China
(NSFC) and a grant from the Ministry of Science and
Technology of the People’s Republic of China.
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