Synthesis of α-Manp-(1→2)-α-Manp-(1→3)-α-Manp-(1→3)-Manp, the tetrasaccharide repeating unit of Escherichia coli O9a, and α-Manp-(1→2)-α-Manp-(1→2)-α-Manp-(1→3)- α-Manp-(1→3)-Manp, the pentasaccharide repeating unit of E. coli O9 and Klebsiella O3

Article abstract of DOI:10.1016/S0008-6215(02)00011-3

The tetrasaccharide repeating unit of Escherichia coli O9a, α-D-Manp-(1→2)-α-D-Manp-(1→3)-α-D-Manp- (1→3)-D-Manp, and the pentasaccharide repeating unit of E. coli O9 and Klebsiella O3, α-D-Manp-(1→2)-α-D-Manp-(1→2)-α-D-Manp- (1→3)-α-D-Manp-(1→3)-D-Manp, were synthesized as their methyl glycosides. Thus, selective 3-O-allylation of p-methoxyphenyl α-D-mannopyranoside via a dibutyltin intermediate gave p-methoxyphenyl 3-O-allyl-α-D-mannopyranoside (2) in good yield. Benzoylation (→3), then removal of 1-O-methoxyphenyl (→4), and subsequent trichloroacetimidation afforded the 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate (5). Condensation of 5 with methyl 4,6-O-benzylidene-α-D-mannopyranoside (6) selectively afforded the (1→3)-linked disaccharide 7. Benzoylation of 7, debenzylidenation, benzoylation, and deallylation gave methyl 2,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-benzoyl- α-D-mannopyranoside (11) as the disaccharide acceptor. Coupling of 11 with (1→2)-linked mannose disaccharide donor 17 or trisaccharide donor 21, followed by deacylation, furnished the target tetrasaccharide and pentasaccharide, respectively.

Full text of DOI:10.1016/S0008-6215(02)00011-3

Carbohydrate Research 337 (2002) 383–390
www.elsevier.com/locate/carres
Synthesis of a-Manp-(1“2)-a-Manp-(1“3)-a-Manp-(1“3)-Manp,
the tetrasaccharide repeating unit of Escherichia coli O9a, and
a-Manp-(1“2)-a-Manp-(1“2)-a-Manp-(1“3)-a-Manp-(1“3)-
Manp, the pentasaccharide repeating unit of E. coli O9 and
Klebsiella O3
Langqiu Chen, Yuliang Zhu, Fanzuo Kong*
Research Center for Eco-En6ironmental Sciences, Academia Sinica, PO Box 2871, Beijing 100085, PR China
Received 2 November 2001; accepted 28 December 2001
Abstract
The tetrasaccharide repeating unit of Escherichia coli O9a, a-
the pentasaccharide repeating unit of E. coli O9 and Klebsiella O3, a-
Manp-(1“3)- -Manp, were synthesized as their methyl glycosides. Thus, selective 3-O-allylation of p-methoxyphenyl a-
mannopyranoside via a dibutyltin intermediate gave p-methoxyphenyl 3-O-allyl-a-
Benzoylation (“3), then removal of 1-O-methoxyphenyl (“4), and subsequent trichloroacetimidation afforded the 3-O-allyl-
2,4,6-tri-O-benzoyl-a- -mannopyranosyl trichloroacetimidate (5). Condensation of 5 with methyl 4,6-O-benzylidene-a-
mannopyranoside (6) selectively afforded the (1“3)-linked disaccharide 7. Benzoylation of 7, debenzylidenation, benzoylation, and
-mannopyranoside (11) as the
D
-Manp-(1“2)-a-
D
-Manp-(1“3)-a-
D
-Manp-(1“3)-
D-Manp, and
D
-Manp-(1“2)-a-
D
-Manp-(1“2)-a-
D
-Manp-(1“3)-a-
D
-
-
D
D
D
-mannopyranoside (2) in good yield.
D
D-
deallylation gave methyl 2,4,6-tri-O-benzoyl-a-
D
-mannopyranosyl-(1“3)-2,4,6-tri-O-benzoyl-a-
D
disaccharide acceptor. Coupling of 11 with (1“2)-linked mannose disaccharide donor 17 or trisaccharide donor 21, followed by
deacylation, furnished the target tetrasaccharide and pentasaccharide, respectively. © 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Oligosaccharide; Mannose; Regioselective synthesis
O-Specific polysaccharides (O-PS) are a part of lipo-
polysaccharides (LPSs) and covalently bind to lipid A
through the core oligosaccharide portion. The O-PS of
gram-negative bacteria are structurally polymorphic,
and they are utilized as the O antigen for serological
typing. Each O-polysaccharide consists of many repeat-
ing units composed of several sugars with various link-
ages. The Escherichia coli O9a polysaccharide has a
Manp.1 Synthesis of these repeating units is important
for investigation of structure–bioactivity relationships
among oligosaccharides, and this communication will
describe their facile preparation.
As outlined in Scheme 1, p-methoxyphenyl a-D-
mannopyranoside (1), readily obtainable from reaction
of mannose peracetate with p-methoxyphenol in the
presence of BF3·Et2O,2 followed by Zemple´n deacetyla-
tion,3 was chosen as the starting material. Selective
3-O-allylation of 1 was achieved giving 2 in good yield
(65%) using the reported method through a dibutyltin
complex.4 Benzoylation of 2 with benzoyl chloride in
pyridine quantitatively gave 3, and oxidative cleavage
of the p-methoxyphenyl group with CAN went
tetrasaccharide repeating unit, a-
Manp-(1“3)-a- -Manp-(1“3)- -Manp, and the E.
coli O9, and Klebsiella O3 polysaccharides have a pen-
D
-Manp-(1“2)-a-
D-
D
D
tasaccharide repeating unit, a-
D
-Manp-(1“2)-a-
D
-
-
Manp-(1“2)-a- -Manp-(1“3)-a-
D
D
-Manp-(1“3)-
D
smoothly to give 3-O-allyl-2,4,6-tri-O-benzoyl-a-D-
mannopyranose (4) in satisfactory yield (80%).
Trichloroacetimidation of 4 with trichloroacetonitrile in
the presence of potassium carbonate or DBU5 was
* Corresponding author. Tel.: +81-10-62936613; fax:
+81-10-62923563.
E-mail address: fzkong@mail.rcees.ac.cn (F. Kong).
0008-6215/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(02)00011-3

384
L. Chen et al. / Carbohydrate Research 337 (2002) 383–390
carried out readily affording the mannose donor 5 in
high yield (90%). Coupling of 5 with methyl 4,6-O-ben-
ride orthoester 14 (40%). The latter was isolated and
identified by its 1H NMR spectrum giving H-1 at l
5.50–5.47 ppm and CH3 at l 1.78 ppm. Rearrangement
of 14 with Me3SiOTf gave the required disaccharide 15
in high yield. Scheme 2 shows the proposed mechanism
for the disaccharide orthoester formation. Deallylation
of 15, followed by trichloroacetimidation, afforded the
disaccharide donor 17,7 while selective deacetylation
with CH3COCl–MeOH gave the disaccharide acceptor
16.8 The trisaccharide donor 21 was prepared by con-
densation of 16 with perbenzoylated mannosyl
trichloroacetimidate (18) (85%), followed by deallyla-
tion and trichloroacetimidation. Finally, coupling of
the disaccharide acceptor 11 with the disaccharide
donor 17, followed by deacylation in ammonia-satu-
rated methanol, gave the tetrasaccharide 23, while con-
densation of 11 with the trisaccharide donor 21,
followed by deacylation, furnished the pentasaccharide
25. The deacylation was carried out in the ammonia-
saturated solution rather than by Zemple´n deacylation
because of the mildness and completion of
debenzoylation.
zylidene-a- -mannopyranoside (6) selectively gave (1“
D
3)-linked disaccharide 7 (85%). The 3-selectivity was
confirmed by benzoylation of 7 to give 8 showing a
newly emerged doublet of doublets in its 1H NMR
spectrum at l 5.55 ppm with J1,2 1.8 Hz and J2,3 3.2 Hz,
which are the salient features for H-2. Hydrolysis to
remove the benzylidene group, followed by benzoyla-
tion, gave the disaccharide 10 in good yield (90% for
two steps). Deallylation of 10 with PdCl2 in CH3OH6
gave the disaccharide acceptor 11 (90%).
The disaccharide donor 17 was prepared from allyl
2-O-acetyl -3,4,6-tri-O-benzoyl-a-
D-mannopyranosyl-
-mannopyranoside (15),
(1“2)-3,4,6-tri-O-benzoyl-a-
D
which was obtained by the reported method through
self-condensation of 3,4,6-tri-O-benzoyl-1,2-O-ally-
loxyethylidene-a-
-mannopyranose (12).7 It was found
D
that when the amount of Me3SiOTf was less than 5%
equiv of 12, and the reaction time was relatively short
(2 h), the product was a mixture consisting of monosac-
charide 13 (20%), disaccharide 15 (40%), and disaccha-
Scheme 1. Reagents and conditions: (a) Bu2SnO, CH3OH, reflux, 2 h; then AllBr, Bu4NI, C6H6, 60 °C, 24 h. (b) PhCOCl/Pyr, rt.
(c) CAN, CH3CN–H2O, rt, 10 min. (d) CCl3CN, CH2Cl2, K2CO3, rt. (e) Me3SiOTf, CH2Cl2, −42 °C to rt. (f) 80% HOAc–H2O,
rt, 24 h. (g) PdCl2, CH3OH, 40 °C, 4 h. (h) 5% CH3COCl–CH3OH, 40 °C. (i) PdCl2, CH3OH, 40 °C. (j) NH3–CH3OH, rt.

L. Chen et al. / Carbohydrate Research 337 (2002) 383–390
385
Scheme 2.
In summary, a very concise and convergent synthesis
p-Methoxyphenyl 3-O-allyl-h-
D
-mannopyranoside (2).
of the target mannose tetrasaccharide and pentasaccha-
ride was achieved in a regio- and stereoselective way.
Because of its simplicity and efficiency, this method
could be used for construction of higher mannose
oligosaccharides with both a-(1“3) and a-(1“2)
linkages.
—p-Methoxyphenyl a-
D
-mannopyranoside (1) (5.00 g,
17.5 mmol) and Bu2SnO (4.80 g,19.3 mmol) were added
to CH3OH (200 mL), and the mixture was heated under
reflux for 2 h, then concentrated to dryness. The residue
was diluted with benzene (200 mL), and allyl bromide
(18.0 mL, 211 mmol), and Bu4NI (6.46 g, 17.5 mmol)
were added to the mixture. The reaction was carried
out at 60 °C for 24 h at which time TLC (3:1 EtOAc–
CH3OH) indicated that the reaction was complete.
Concentration of the reaction mixture and purification
by column chromatography (EtOAc) gave 2 as a syrup
1. Experimental
General methods.—Melting points were determined
with a ‘Mel-Temp’ apparatus. Optical rotations were
determined with a Perkin–Elmer model 241-MC auto-
matic polarimeter for solutions in a 1-dm, jacketed cell.
1H NMR spectra were recorded with Varian XL-400
and Varian XL-200 spectrometers, for solutions in
CDCl3 with tetramethylsilane (Me4Si) as the internal
standard. Chemical shifts are expressed in ppm
downfield from the internal Me4Si absorption. Mass
spectra were recorded with a VG PLATFORM mass
spectrometer using the electrospray-ionization mode.
Thin-layer chromatography (TLC) was performed on
silica gel HF with detection by charring with 30% (v/v)
H2SO4 in MeOH or by UV detection. Column chro-
matography was conducted by elution of a column
(8×100 mm, 16×240 mm, 18×300 mm, and 35×400
mm) of silica gel (100–200 mesh) and EtOAc–
petroleum ether (bp 60–90 °C) as the eluent. Analytical
LC was performed with a Gilson HPLC consisting of a
pump (model 306), stainless steel column packed with
silica gel (Spherisorb SiO2, 10×300 mm or 4.6×250
mm), differential refractometer (132-RI detector) and
UV–vis detector (model 118). EtOAc–petroleum ether
(bp 60–90 °C) was used as the eluent at a flow rate of
1–4 mL/min. Solutions were concentrated at a temper-
ature B60 °C under diminished pressure.
1
(3.70 g, 65%): [h]D20 +95.4° (c 1.1, CHCl3); H NMR
(CDCl3): l 6.98 (d, 2 H, J 9.1 Hz, p-CH3OPhH), 6.82
(d, 2 H, J 9.1 Hz, p-CH3OPhH), 6.00 (m, 1 H,
CH2ꢀCHꢁCH2ꢁ), 5.51 (d, 1 H, J1,2 1.6 Hz, H-1), 5.40–
5.25 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.30–4.16 (m, 2 H,
CH2ꢀCHꢁCH2ꢁ), 4.21 (m, 1 H), 4.11 (dd, 1 H, J3,4
=
J4,5=9.5 Hz, H-4), 3.91–3.87 (dd, 1 H, J5,6 3.2, J6,6%
12.3 Hz, H-6), 3.86–3.83 (dd, 1 H, J2,3 3.2, J3,4 9.5 Hz,
H-3), 3.78–3.73 (m, 2 H), 3.77 (s, 3 H, CH3), 2.98 (br,
3 H, OH). Anal. Calcd for C16H22O7: C, 58.90; H, 6.75.
Found: C, 58.61; H, 6.77.
p-Methoxyphenyl 3-O-allyl-2,4,6-tri-O-benzoyl-h-D-
mannopyranoside (3).—To a solution of 2 (3.26 g, 10.0
mmol) in pyridine (8 mL), BzCl (4.17 mL, 36.0 mmol)
was added dropwise, and the mixture was stirred
overnight at rt, at which time TLC (3:1 petroleum
ether–EtOAc) indicated that the reaction was complete.
The mixture was diluted with CH2Cl2, and washed with
1 N HCl, water, and satd aq NaHCO3. The organic
layers were combined, dried, and concentrated. Purifi-
cation by column chromatography (3:1 petroleum
ether–EtOAc) gave 3 quantitatively as a syrup (6.38 g,
1
100%): [h]2D0 +19.1° (c 1.0, CHCl3); H NMR (CDCl3):
l 8.12–7.38 (m, 15 H, PhH), 7.08 (d, 2 H, J 9.1 Hz,
p-CH3OPhH), 6.76 (d, 2 H, J 9.1 Hz, p-CH3OPhH),

386
L. Chen et al. / Carbohydrate Research 337 (2002) 383–390
5.86 (t, 1 H, J3,4=J4,5=9.8 Hz, H-4), 5.79–5.69 (m, 2
H, H-2, CH2ꢀCHꢁCH2ꢁ), 5.61 (d, 1 H, J1,2 1.8 Hz,
H-1), 5.23–5.06 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.63–4.61
(m, 1 H), 4.45–4.42 (m, 2 H), 4.38–4.34 (dd, 1 H, J2,3
ture was stirred for 3 h, at the end of which time TLC
indicated that the reaction was complete. Then the
mixture was neutralized with triethylamine and concen-
trated under reduced pressure to dryness. Purification
by column chromatography (2:1 petroleum ether–
EtOAc) gave 7 as a syrup (3.89 g, 85%): [h]2D0 −0.8° (c
3.3, J3,4 9.8 Hz, H-3), 4.22–4.04 (m,
2
H,
CH2ꢀCHꢁCH2ꢁ), 3.73 (s, 3 H, CH3). Anal. Calcd for
C37H34O10: C, 69.59; H, 5.33. Found: C, 69.92; H, 5.31.
1
1.0, CHCl3); H NMR (CDCl3): l 8.08–7.27 (m, 20 H,
3-O-Allyl-2,4,6-tri-O-benzoyl-h-
D
-mannopyranose
PhH), 5.80–5.63 (m, 4 H, H-4II, CH2ꢀCHꢁCH2ꢁ, H-2II,
PhCHꢀ), 5.47 (d, 1 H, J1,2 1.7 Hz, H-1II), 5.15–5.00 (m,
2 H, CH2ꢀCHꢁCH2ꢁ), 4.69 (s, 1 H, H-1I), 4.66–4.63
(m, 2 H), 4.47–4.40 (m, 1 H), 4.31–4.23 (m, 2 H),
4.17–4.09 (m, 3 H), 4.00–3.96 (m, 2 H), 3.89–3.80 (m,
1 H), 3.29 (s, 3 H, CH3), 2.07 (br, 1 H, OH). Anal.
Calcd for C44H44O14: C, 66.33; H, 5.53. Found: C,
66.60; H, 5.51.
(4).—To a solution of 3 (6.38 g, 10.0 mmol) in 4:1
CH3CN–water (600 mL) was added CAN ((NH4)2-
Ce(NO3)6, 21.93 g, 40.0 mmol), and the mixture was
stirred for 10 min at rt, at the end of which time TLC
(3:1 petroleum ether–EtOAc) indicated that the reac-
tion was complete. The mixture was extracted with
EtOAc and washed with satd aq NaHCO3. The organic
layer was concentrated under reduced pressure and
purified by column chromatography (3:1 petroleum
ether–EtOAc) to afford 4 as a syrup (4.26 g, 80%): [h]D20
Methyl 3-O-allyl-2,4,6-tri-O-benzoyl-h-D-mannopy-
ranosyl-(1“3)-2-O-benzoyl-4,6-O-benzylidene-h-
D
-
mannopyranoside (8).—To a solution of 7 (3.98 g, 5.0
mmol) in pyridine (3 mL), BzCl (0.7 mL, 6.0 mmol)
was added dropwise, and the mixture was stirred
overnight at rt, at which time TLC (2:1 petroleum
ether–EtOAc) indicated that the reaction was complete.
The mixture was diluted with CH2Cl2, washed with 1 N
HCl, water, and satd aq NaHCO3. The organic layer
was combined, dried, and concentrated. Purification by
column chromatography (2:1 petroleum ether–EtOAc)
gave 8 quantitatively as a syrup (4.50 g, 100%): [h]D20
1
−31.6° (c 1.1, CHCl3); H NMR (CDCl3): l 8.11–7.34
(m, 15 H, PhH), 5.88 (dd, 1 H, J3,4=J4,5=9.8 Hz,
H-4), 5.73–5.66 (m, 1 H, CH2ꢀCHꢁCH2ꢁ), 5.61 (dd, 1
H, J1,2 1.8, J2,3 3.2 Hz, H-2), 5.44 (d, 1 H, J1,2 1.8 Hz,
H-1), 5.19–5.03 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.74–4.70
(dd, 1 H, J 2.6, J 12.1 Hz), 4.52–4.48 (m, 1 H, H-5),
4.39–4.35 (dd, 1 H, J 4.1, J 12.1 Hz), 4.25–4.21 (dd, 1
H, J2,3 3.2, J3,4 9.8 Hz, H-3), 4.15–3.97 (m, 2 H,
CH2ꢀCHꢁCH2ꢁ), 3.50 (br, 1 H, OH). Anal. Calcd for
C30H28O9: C, 67.67; H, 5.26. Found: C, 67.34; H, 5.27.
1
−57.7° (c 0.9, CHCl3); H NMR (CDCl3): l 8.19–7.26
3-O-Allyl-2,4,6-tri-O-benzoyl-h-
D
-mannopyranosyl
(m, 25 H, Ph), 5.76 (dd, 1 H, J3,4=J4,5=9.9 Hz,
H-4II%), 5.73 (s, 1 H, PhCHꢀ), 5.66 (dd, 1 H, J1,2 1.3, J2,3
3.8 Hz, H-2I), 5.55 (dd, 1 H, J1,2 1.8, J2,3 3.2 Hz, H-2II),
5.49 (m, 1 H, CH2ꢀCHꢁCH2ꢁ), 5.44 (d, 1 H, J1,2 1.8
Hz, H-1II), 4.84 (d, 1 H, J1,2 1.3 Hz, H-1I), 4.82–4.67
(m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.68 (m, 1 H), 4.51 (dd, 1 H,
J2,3 3.8, J3,4 9.5 Hz, H-3I), 4.48–4.35 (m, 3 H), 4.21 (dd,
1 H, J3,4=J4,5=9.5 Hz, H-4I), 3.94–3.90 (m, 3 H),
3.89–3.71 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 3.37 (s, 3 H,
CH3); 13C NMR (CDCl3): l 166.23, 165.68, 165.45,
165.28 (4 PhCO), 136.95, 133.92, 133.57, 133.54,
133.13, 132.77 (5 Ph, CH2ꢀCHꢁCH2ꢁ), 130.09, 129.85,
129.68, 129.62, 129.56, 128.75, 128.63, 128.35, 128.26,
128.11, 125.87 (5 Ph), 117.22 (CH2ꢀCHꢁCH2ꢁ), 101.32
(PhCHꢀ), 99.80, 98.50 (C-1), 79.30 (C-3), 73.91, 71.82,
71.15, 70.61, 69.47, 68.88, 68.70, 68.15, 63.35, 63.26
(C-2,3,4,5,6, CH2ꢀCHꢁCH2ꢁ), 55.11 (CH3). Anal.
Calcd for C51H48O15: C, 68.00; H, 5.33. Found: C,
68.25; H, 5.30.
trichloroacetimidate (5).—Compound 4 (9.00 g, 16.9
mmol) was dissolved in CH2Cl2 (80 mL), then
trichloroacetonitrile (5 mL) and anhyd K2CO3 (9.00 g)
were added. The reaction mixture was stirred overnight
at rt, at the end of which time TLC (3:1 petroleum
ether–EtOAc) indicated that the reaction was complete.
Concentration of the reaction mixture, followed by
purification on a silica-gel column with 3:1 petroleum
ether–EtOAc as the eluent, gave the monosaccharide
donor 5 as foamy solid (10.30 g, 90%): 1H NMR
(CDCl3): l 8.81 (s, NHꢀ), 8.11–7.27 (m, 15 H, PhH),
6.49 (d, 1 H, J1,2 1.6 Hz, H-1), 5.95 (dd, 1 H, J3,4
4,5=9.8 Hz, H-4), 5.79 (dd, 1 H, J1,2 1.6, J2,3 3.3 Hz,
=
J
H-2), 5.70 (m, 1 H, CH2ꢀCHꢁCH2ꢁ), 5.26–5.08 (m, 2
H, CH2ꢀCHꢁCH2ꢁ), 4.70–4.67 (dd, 1 H, J 1.6, J 11.7
Hz, H-6), 4.47–4.40 (m, 2 H, H-5, H-6), 4.27–4.24 (dd,
1 H, J2,3 3.3, J3,4 9.8 Hz, H-3), 4.18–4.01 (m, 2 H,
CH2ꢀCHꢁCH2ꢁ). Anal. Calcd for C32H28Cl3NO9: C,
56.76; H, 4.14. Found: C, 56.60; H, 4.15.
Methyl 3-O-allyl-2,4,6-tri-O-benzoyl-h-D-mannopy-
Methyl 3-O-allyl-2,4,6-tri-O-benzoyl-h-
ranosyl-(1“3)-4,6-O-benzylidene-h- -mannopyranoside
(7).—Trichloroacetimidate 5 (3.38 g, 5.0 mmol) and
methyl 4, 6-O-benzylidene-a- -mannopyranoside (6)
(1.41 g, 5.0 mmol) were dried together under high
vacuum for 2 h, then dissolved in anhyd CH2Cl2 (70
mL), Me3SiOTf (40 mL, 0.21 mmol) was added drop-
wise at −42 °C with N2 protection. The reaction mix-
D
-mannopy-
ranosyl-(1“3)-2-O-benzoyl-h- -mannopyranoside (9).
D
D
—Compound 8 (2.25 g, 2.5 mmol) was dissolved in
80% AcOH (50 mL), and the mixture was stirred at
50 °C for 24 h, at the end of which time TLC (2:1
petroleum ether–EtOAc) indicated that the reaction
was complete. The mixture was concentrated under
reduced pressure, and the residue was passed through a
silica gel column with 2:1 petroleum ether–EtOAc as
D

L. Chen et al. / Carbohydrate Research 337 (2002) 383–390
387
the eluent to give 9 as foamy solid (1.83 g, 90%): [h]D20
−31.2° (c 0.8, CHCl3); H NMR (CDCl3): l 8.16–7.32
129.27, 129.08, 128.97, 128.73, 128.46, 128.37, 128.32,
128.28 (6 Ph), 99.41, 98.52 (C-1), 75.79 (C-3), 72.33,
71.71, 69.78, 69.24, 68.72, 68.55, 68.40, 62.99, 62.75
(C-2,3,4,5,6), 55.39 (CH3). Anal. Calcd for C55H48O17:
C, 67.35; H, 4.90, Found: C, 67.30; H, 4.91.
1
(m, 20 H, PhH), 5.77 (dd, 1 H, J3,4=J4,5=9.7 Hz,
H-4II), 5.56–5.45 (m, 4 H, H-2II, H-2I, CH2ꢀCHꢁCH2ꢁ,
H-1II), 4.90–4.75 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.83 (d, 1
H, J1,2 1.3 Hz, H-1I), 4.65–4.62 (m, 1 H), 4.40–4.33 (m,
2 H), 4.28–4.26 (m, 2 H), 3.97–3.94 (m, 3 H), 3.93–
3.71 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 3.72 (m, 1 H, H-5II),
3.35 (s, 3 H, CH3), 2.46 (br, 2 H, OH). Anal. Calcd for
C44H44O15: C, 65.02; H, 5.42. Found: C, 65.31; H, 5.40.
Allyl 2-O-acetyl-3,4,6-tri-O-benzoyl-h-
ranosyl-(1“2)-3,4,6-tri-O-benzoyl-h- -mannopyrano-
side (15).—3,4,6-Tri-O-benzoyl-a- -mannopyranose
D-mannopy-
D
D
1,2-(allyl orthoacetate)7 (12, 1.25 g, 2.2 mmol) was
dried under high vacuum for 2 h, then dissolved in
anhyd CH2Cl2 (30 mL), Me3SiOTf (6.0 mL, 0.031
mmol) was added dropwise at −42 °C with N2 protec-
tion. The reaction mixture was stirred for 3 h, at the
end of which time TLC indicated that the reaction was
complete. Then the mixture was neutralized with tri-
ethylamine and concentrated to a syrup. Purification by
column chromatography (3:1 petroleum ether–EtOAc)
Methyl 3-O-allyl-2,4,6-tri-O-benzoyl-h-D-mannopy-
ranosyl-(1“3)-2,4,6-tri-O-benzoyl-h- -mannopyrano-
D
side (10).—To a solution of 9 (3.17 g, 3.9 mmol) in
pyridine (4 mL), BzCl (1.1 mL, 9.5 mmol) was added
dropwise, and the mixture was stirred overnight at rt, at
which time TLC (2:1 petroleum ether–EtOAc) indi-
cated that the reaction was complete. The mixture was
diluted with CH2Cl2 and washed with 1 N HCl, water
and satd aq NaHCO3. The organic layer was combined,
dried, and concentrated. Purification by column chro-
matography (2:1 petroleum ether–EtOAc) gave 10
quantitatively as a syrup (3.98 g, 100%): [h]2D0 −32.9° (c
gave 15 (0.36 g) and 3,4,6-tri-O-benzoyl-a-
ranose 1,2-(allyl 3,4,6-tri-O-benzoyl-a- -mannopyran-
osid-2-yl orthoacetate) (14, 0.36 g), and allyl 2-O-
acetyl-3,4,6-tri-O-benzoyl-a- -mannopyranoside (13,
D-mannopy-
D
D
0.18 g). Compound 14 (0.60 g, 0.57 mmol) was easily
converted to 15 (0.54 g, 90%) with Me3SiOTf (0.1
equiv) by the same procedure as described in the prepa-
ration of 14 from 12. For 14: [h]2D0 −20.8° (c 1.3,
CHCl3); 1H NMR (CDCl3): l 8.01–7.26 (m, 30 H,
PhH), 5.88 (dd, 1 H, J3,4=J4,5=10.1 Hz, H-4II), 5.83
(dd, 1 H, J3,4=J4,5=9.8 Hz, H-4I), 5.78 (m, 1 H,
CH2ꢀCHꢁCH2ꢁ), 5.55–5.52 (dd, 1 H, J2,3 3.7, J3,4 10.1
Hz, H-3II), 5.50–5.47 (m, 2 H, H-3I, H-1II), 5.16–4.91
(m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.94 (d, 1 H, J1,2 1.4 Hz,
H-1I), 4.83 (dd, 1 H, J1,2 2.8, J2,3 3.7 Hz, H-2II),
4.57–4.51 (m, 2 H), 4.44–4.36 (m, 3 H), 4.29–4.24 (m,
1 H), 4.13–3.88 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 3.97 (m, 1
H, H-5), 1.78 (s, 3 H, CH3). Anal. Calcd for C59H52O18:
C, 67.56; H, 4.96. Found: C, 67.67; H, 4.89. For 15:
[h]2D0 +3.0° (c 1.3, CHCl3); 1H NMR (CDCl3): l
1
0.9, CHCl3); H NMR (CDCl3): l 8.11–7.25 (m, 30 H,
PhH), 5.97 (dd, 1 H, J3,4=J4,5=10.0 Hz, H-4II), 5.72
(dd, 1 H, J3,4=J4,5=9.9 Hz, H-4I), 5.67 (dd, 1 H, J1,2
1.7, J2,3 3.1 Hz, H-2II), 5.41 (m, 1 H, CH2ꢀCHꢁCH2ꢁ),
5.21–5.18 (m, 2 H, H-1II, H-2), 4.95 (d, 1 H, H-1I, J1,2
1.4 Hz), 4.87–4.72 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 4.70–
4.66 (dd, 1 H, J 2.6, J 12.1 Hz), 4.61–4.57 (m, 2 H),
4.52–4.48 (dd, 1 H), 4.35–4.26 (m, 3 H), 3.89–3.86 (dd,
1 H), 3.76–3.59 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 3.42 (s, 3 H,
CH3). Anal. Calcd for C58H52O17: C, 68.24; H, 5.10.
Found: C, 68.30; H, 5.07.
Methyl
2,4,6-tri-O-benzoyl-h-D-mannopyranosyl-
(1“3)-2,4,6-tri-O-benzoyl-h-
D
-mannopyranoside (11).
—To a solution of 10 (2.04 g, 2.0 mmol) in anhyd
CH3OH (70 mL) was added PdCl2 (0.2 g), and the
mixture was stirred for 4 h at 40 °C, at the end of which
time TLC (2:1 petroleum ether–EtOAc) indicated that
the reaction was complete. The mixture was filtrated,
the filtrate was concentrated, and the residue was
passed over a silica-gel column with 2:1 petroleum
ether–EtOAc as the eluent to give 11 as a syrup (1.76 g,
8.01–7.33 (m, 30 H, PhH), 5.97 (dd, 1 H, J3,4=J4,5
=
9.9 Hz, H-4II), 5.91–5.82 (m, 4 H, CH2ꢀCHꢁCH2ꢁ,
H-4I, H-3II, H-3I), 5.69 (dd, 1 H, H-2II), 5.28–5.17 (m,
2 H, CH2ꢀCHꢁCH2ꢁ), 5.15 (d, 1 H, J1,2 1.7 Hz, H-1II),
5.09 (d, 1 H, J1,2 1.4 Hz, H-1I), 4.63–4.44 (m, 5 H, 4
H-6, H-5II), 4.39–4.35 (m, 2 H, H-2I, H-5I), 4.20–3.89
(m, 2 H, CH2ꢀCHꢁCH2ꢁ). Anal. Calcd for C59H52O18:
C, 67.56; H, 4.96. Found: C, 67.63; H, 4.90.
1
90%): [h]2D0 −27.4° (c 0.8, CHCl3); H NMR (CDCl3):
l 8.18–7.28 (m, 30 H, PhH), 5.97 (dd, 1 H, J3,4=J4,5
=
10.0 Hz, H-4II), 5.65 (dd, 1 H, J1,2 1.2, J2,3 3.1 Hz,
H-2II), 5.59 (dd, 1 H, J3,4=J4,5=9.7 Hz, H-4I), 5.27 (d,
1 H, J1,2 1.2 Hz, H-1II), 5.07 (dd, 1 H, J1,2 1.4, J2,3 3.1
Hz, H-2I), 4.94 (d, 1 H, J1,2 1.4 Hz, H-1I), 4.71–4.67
(dd, 1 H, J 2.5, J 12.1 Hz), 4.61–4.57 (m, 2 H),
4.48–4.44 (dd, 1 H, J 4.5, J 12.2 Hz), 4.40–4.34 (m, 2
H), 4.27–4.24 (m, 1 H), 4.19–4.16 (dd, 1 H, J 3.2, J 9.8
Hz), 3.42 (s, 3 H, CH3), 2.40 (br, 1 H, OH); 13C NMR
(CDCl3): l 166.39, 166.14, 166.06, 165.73, 165.60,
165.07 (6 PhCO), 133.60, 133.41, 133.25, 132.98,
132.87, 129.91, 129.89, 129.83, 129.76, 129.69, 129.62,
Allyl 3,4,6-tri-O-benzoyl-h-
D
-mannopyranosyl-(1“
2)-3,4,6-tri-O-benzoyl-h- -mannopyranoside (16).—To
D
a solution of 15 (1.00 g, 0.95 mmol) in anhyd CH3OH
(30 mL) was added CH3COCl (1.5 mL), and the mix-
ture was stirred for 3–4 h at 40 °C, at the end of which
time TLC (2:1 petroleum ether–EtOAc) indicated that
the reaction was complete. The mixture was concen-
trated under reduced pressure, then passed through a
silica-gel column with 2:1 petroleum ether–EtOAc as
the eluent to gave 16 as a syrup (0.82 g, 85%): [h]D20
1
+0.1° (c 0.8, CHCl3); H NMR (CDCl3): l 8.08–7.33

388
L. Chen et al. / Carbohydrate Research 337 (2002) 383–390
(m, 30 H, PhH), 5.98 (dd, 1 H, J3,4=J4,5=9.9 Hz,
H-4II), 5.92 (dd, 1 H, J3,4=J4,5=9.8 Hz, H-4I), 5.88
(m, 1 H, CH2ꢀCHꢁCH2ꢁ), 5.82 (dd, 1 H, J2,3 3.1, J3,4
9.9 Hz, H-3II), 5.78 (dd, 1 H, J2,3 3.1, J3,4 9.8 Hz, H-3I),
5.29–5.15 (m, 2 H, CH2ꢀCHꢁCH2ꢁ), 5.18 (d, 1 H, J1,2
1.1 Hz, H-1II), 5.15 (d, 1 H, J1,2 1.8 Hz, H-1I), 4.63–
4.59 (m, 1 H), 4.57–4.35 (m, 5 H), 4.50 (m, 1 H, H-2),
4.41 (m, 1 H, H-2), 4.21–3.91 (m, 2 H, CH2ꢀCHꢁ
CH2ꢁ), 2.40 (br, 1 H, OH); 13C NMR (CDCl3): l
166.23, 166.06, 165.58, 165.52, 165.28, 165.09 (PhCO),
133.33, 133.25, 133.14, 132.95, 129.81, 129.72, 129.64,
129.59, 129.16, 128.96, 128.91, 128.84, 128.48, 128.36,
128.28, 117.94 (CH2ꢀCHꢁCH2ꢁ), 101.48, 97.89 (C-1),
72.15, 71.27, 69.58, 69.29, 68.79, 68.65, 67.34, 66.83,
63.61, 63.41. Anal. Calcd for C57H50O17: C, 67.99; H,
4.97. Found: C, 68.29; H, 4.95.
gel column with 2:1 petroleum ether–EtOAc as the
eluent to gave 20 as a syrup (0.50 g, 90%): [h]2D0 −28.2°
(c 0.8, CHCl3); H NMR (CDCl3): l 8.08–7.11 (m, 50
1
H, PhH), 6.00–5.90 (m, 5 H, H-4III, H-4II, H-4I, H-3III,
H-3II), 5.79–5.74 (m, 2 H, H-3I, H-2III), 5.51 (d, 1 H,
H-1III), 5.42 (d, 1 H, H-1II), 4.96 (s, 1 H, H-1I), 4.64–
4.45 (m, 8 H), 4.39 (m, 1 H, H-2I), 4.33 (m, 1 H),
4.20–4.16 (dd, 1 H, J5,6 4.25, J6,6% 12.2 Hz, H-6I), 2.85
(br,1 H, OH). Anal. Calcd for C88H72O26: C, 68.39; H,
4.66. Found: C, 68.66; H, 4.64.
2,3,4,6-Tetra-O-benzoyl-h-
3,4,6-tri-O-benzoyl-h- -mannopyranosyl-(1“2)-3,4,6-
tri-O-benzoyl-h- -mannopyranosyl trichloroacetimidate
D
-mannopyranosyl-(1“2)-
D
D
(21).—Compound 20 (0.95 g, 0.62 mmol) was dissolved
in CH2Cl2 (40 mL), then trichloroacetonitrile (3 mL)
and anhyd K2CO3 (0.95 g) were added. The reaction
mixture was stirred overnight at rt, at the end of which
time TLC (2:1 petroleum ether–EtOAc) indicated that
the reaction was complete. Concentration of the reac-
tion mixture, followed by purification on a silica-gel
column with 3:1 petroleum ether–EtOAc as the eluent,
gave the trisaccharide donor 21 as foamy solid (0.94 g,
Allyl
(1“2)-3,4,6-tri-O-benzoyl-h-
3,4,6-tri-O-benzoyl-h- -mannopyranoside
4,6-Tetra-O-benzoyl-a- -mannopyranosyl trichloroace-
2,3,4,6-tetra-O-benzoyl-h-
-mannopyranosyl-(1“2)-
(19).—2,3,
D-mannopyranosyl-
D
D
D
timidate (18, 0.67 g, 0.9 mmol) and 16 (0.60 g, 0.6
mmol) were dried together under high vacuum for 2 h,
then dissolved in anhyd CH2Cl2 (40 mL). Me3SiOTf (10
mL, 0.053 mmol) was added dropwise at −42 °C with
N2 protection. The reaction mixture was stirred for 3 h,
at the end of which time TLC indicated that the
reaction was complete. Then the mixture was neutral-
ized with triethylamine and concentrated under reduced
pressure to dryness. Purification by column chromatog-
raphy (2:1 petroleum ether–EtOAc) gave 19 as a syrup
1
90%): H NMR (CDCl3): l 8.75 (s, 1 H, HNꢀ), 8.08–
7.11 (m, 50 H, PhH), 6.61 (d, 1 H, J1,2 2.4 Hz, H-1I),
6.09–5.92 (m, 5 H, H-4III, H-4II, H-4I, H-3III, H-3II),
5.85–5.80 (m, 2 H, H-3I, H-2III), 5.57 (s, 1 H, H-1III),
5.05 (s, 1 H, H-1II), 4.75 (m, 1 H, H-2II), 4.70 (dd, 1 H,
J5,6 2.3, J6,6% 11.7 Hz, H-6III), 4.67–4.47 (m, 7 H), 4.39
(m, 1 H, H-5I), 4.17 (m, 1 H, H-6I). Anal. Calcd for
C90H72Cl3NO26: C, 63.96; H, 4.26. Found: C, 63.74; H,
4.28.
1
(0.80 g, 85%): [h]D20 +7.5° (c 1.0, CHCl3); H NMR
(CDCl3): l 8.08–7.11 (m, 50 H, PhH), 6.00–5.88 (m, 5
H), 5.95 (m,1 H, CH2ꢀCHꢁCH2ꢁ), 5.74–5.70 (m, 2 H,
H-2III, H-3I), 5.41 (d,1 H, H-1III), 5.32–5.20 (m, 2 H,
CH2ꢀCHꢁCH2ꢁ), 5.12 (d, 1 H, H-1II), 4.92 (d, 1 H,
H-1I), 4.62–4.52 (m, 5 H), 4.49–4.43 (m, 2 H, H-2I,
H-5I), 4.23–3.96 (m, 1 H, CH2ꢀCHꢁCH2ꢁ), 4.18 (m, 1
H, H-6I); 13C NMR (CDCl3): l 166.21, 166.12, 165.77,
165.51, 165.48, 165.28, 165.28, 165.14, 164.86, 164.63
(PhCO), 133.36, 133.25, 133.18, 133.15, 133.09, 132.95,
132.88, 129.97, 129.91, 129.81, 129.73, 129.60, 129.56,
129.18, 129.09, 128.98, 128.92, 128.88, 128.84, 128.73,
128.59, 128.45, 128.37, 128.32, 128.27, 128.24, 128.20,
117.90 (CH2ꢀCHꢁCH2ꢁ), 99.95, 99.56, 97.98 (C-1),
71.16, 70.07, 69.94, 69.65, 69.55, 68.73, 68.63, 67.39,
66.44, 63.75, 63.56, 62.88. Anal. Calcd for C91H76O26:
C, 68.94; H, 4.80. Found: C, 68.65; H, 4.82.
Methyl 2-O-acetyl-3,4,6-tri-O-benzoyl-h-
ranosyl-(1“2)-3,4,6-tri-O-benzoyl-h- -mannopyran-
osyl-(1“3)-2,4,6-tri-O-benzoyl-h- -mannopyranosyl-
(1“3)-2,4,6-tri-O-benzoyl-h- -mannopyranoside (22).
—2-O-Acetyl-3,4,6-tri-O-benzoyl-a- -mannopyranosyl-
(1“2)-3,4,6-tri-O-benzoyl-a- -mannopyranosyl tri-
D-mannopy-
D
D
D
D
D
chloroacetimidate9 (17, 0.23 g, 0.2 mmol) and 11 (0.20 g,
0.2 mmol) were dried together under high vacuum
for 2 h, then dissolved in anhyd CH2Cl2 (20 mL).
Me3SiOTf (6.0 mL, 0.031 mmol) was added dropwise at
−42 °C with N2 protection. The reaction mixture was
stirred for 3 h, at the end of which time TLC indicated
that the reaction was complete. The mixture was then
neutralized with triethylamine and concentrated under
reduced pressure to a syrup. Purification by column
chromatography (2:1 petroleum ether–EtOAc) gave 22
as foamy solid (0.39 g, 90%): [h]2D0 −6.2° (c 0.7,
CHCl3); 1H NMR (CDCl3): l 8.08–7.24 (m, 60 H,
PhH), 6.01 (dd, 1 H, J3,4=J4,5=10.0 Hz, H-4IV), 5.91–
5.82 (m, 3 H, H-4III, H-4II, H-4I), 5.79–5.75 (m, 1 H,
H-3IV), 5.68 (m, 1 H, H-2IV), 5.56–5.52 (dd, 1 H, J2,3
3.1, J3,4 10.0 Hz, H-3III), 5.49 (m, 1 H, H-2III), 5.34 (s,
1 H, H-1IV), 5.31 (m, 1 H, H-2II), 5.15 (s, 1 H, H-1III),
4.95 (d, 1 H, J1,2 1.0 Hz, H-1II), 4.69–4.66 (m, 1 H),
4.65 (s, 1 H, H-1I), 4.63–4.60 (dd, 1 H, J 3.3, J 9.8 Hz),
2,3,4,6-Tetra-O-benzoyl-h-
3,4,6-tri-O-benzoyl-h- -mannopyranosyl-(1“2)-3,4,6-
tri-O-benzoyl-h- -mannopyranose (20).—To a solution
D
-mannopyranosyl-(1“2)-
D
D
of 19 (0.57 g, 0.36 mmol) in anhyd CH3OH (30 mL)
was added PdCl2 (0.30 g), and the mixture was stirred
for 4 h at 40 °C, at the end of which time TLC (2:1
petroleum ether–EtOAc) indicated that the reaction
was complete. The mixture was filtered, the filtrate was
concentrated, and the residue was passed over a silica-

L. Chen et al. / Carbohydrate Research 337 (2002) 383–390
389
4.59–4.55 (dd, 1 H, J 2.2, J 12.3 Hz), 4.49–4.46 (m, 2
H), 4.35 (m, 1 H), 4.32–4.18 (m, 3 H), 4.13–4.08 (m, 3
H), 4.00–3.95 (m, 3 H), 3.44 (s, 3 H, CH3O), 1.96 (s, 3
H, CH3CO); 13C NMR (CDCl3): l 168.87 (CH3CO),
166.08, 166.03, 165.97, 165.83, 165.68, 165.63, 165.34,
165.15, 164.85, 164.81, 164.81, 164.58 (12 PhCO),
133.65, 133.59, 133.59, 133.30. 133.25, 133.07, 132.99,
132.93, 132.83, 132.79, 132.61, 129.90, 129.80, 129.78,
129.71, 129.66, 129.62, 129.56, 129.28, 129.15, 129.00,
128.92, 128.87, 128.85, 128.75, 128.60, 128.54, 128.39,
128.35, 128.32, 128.27, 128.01 (Ph), 100.38, 99.49,
99.08, 98.49 (C-1), 77.18, 76.75 (C-3), 76.17, 75.45,
71.74, 71.44, 70.42, 69.63, 69.60, 69.41, 69.38, 69.12,
68.67, 68.30, 68.00, 66.51, 66.44, 62.95, 62.68, 62.49,
62.00 (C-2,3,4,5,6), 55.43 (CH3O), 20.42 (CH3CO).
Anal. Calcd for C111H94O34: C, 67.61; H, 4.77. Found:
C, 67.29; H, 4.78.
(C-2, 3, 4, 5, 6), 55.45 (CH3O). Anal. Calcd for
143H118O42: C, 68.48; H, 4.71. Found: C, 68.69; H,
4.69.
Methyl h-
ranosyl-(1“3)-h-
C
D
-mannopyranosyl-(1“2)-h-
D
-mannopy-
-man-
D
-mannopyranosyl-(1“3)-h-
D
nopyranoside (23).—Compound 22 (0.23 g, 0.12 mmol)
was dissolved in a satd solution of NH3 in anhyd
CH3OH (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 23 as a syrup (75 mg, 90%): [h]2D0 +6.0° (c 0.9,
CHCl3); 1H NMR (D2O): l 5.25 (s, 1 H, H-1IV), 4.96 (s,
1 H, H-1III), 4.92 (s, 1 H, H-1II), 4.61 (s, 1 H, H-1I),
4.09 (m, 1 H), 3.97–3.94 (d, 3 H), 3.88–3.85 (m, 2 H),
3.80–3.70 (m, 7 H), 3.66–3.50 (m, 12 H), 3.28 (s, 3 H,
CH3); 13C NMR (D2O): l 104.86, 104.81, 103.32,
103.27 (C-1), 80.99, 76.04, 75.79, 72.90, 72.54, 72.12,
68.64, 63.49, 63.40, 57.32 (CH3). MALDI-TOFMS
Calcd for C25H44O21: [M] 680.2, Found: [M+Na]
703.6.
Methyl 2,3,4,6-tetra-O-benzoyl-h-
(1“2)-3,4,6-tri-O-benzoyl-h- -mannopyranosyl-(1“2)-
3,4,6-tri-O-benzoyl-h- -mannopyranosyl-(1“3)-2,4,6-
tri-O-benzoyl-h- -mannopyranosyl-(1“3)-2,4,6-tri-O-
benzoyl-h- -mannopyranoside (24).—Donor 21 (0.34 g,
D-mannopyranosyl-
D
D
D
Methyl h-
ranosyl - (1“2) - h -
mannopyranosyl-(1“3)-h-
D
-mannopyranosyl-(1“2)-h-
- mannopyranosyl - (1“3) - h -
-mannopyranoside (25).—
D-mannopy-
D
D
D-
0.20 mmol) and acceptor 11 (0.20 g, 0.2 mmol) were
dried together under high vacuum for 2 h, then dis-
solved in anhyd CH2Cl2 (25 mL). Me3SiOTf (6.0 mL,
0.031 mmol) was added dropwise at −42 °C with N2
protection. The reaction mixture was stirred for 3 h, at
the end of which time TLC indicated that the reaction
was complete. Then the mixture was neutralized with
triethylamine and concentrated under reduced pressure
to dryness. Purification by column chromatography
(2:1 petroleum ether–EtOAc) gave 24 as a syrup
D
Compound 24 (0.10 g, 0.04 mmol) was dissolved in a
satd solution of NH3 in anhyd CH3OH (5 mL). After a
week at rt, the reaction mixture was concentrated, and
the residue was purified by chromatography on Sep-
hadex LH-20 (MeOH) to afford 25 as a syrup (31 mg,
1
90%): [h]2D0 +47.1° (c 0.8, CHCl3); H NMR (D2O): l
5.25 (s, 1 H, H-1V), 5.18 (s, 1 H, H-1IV), 4.96 (s, 1 H,
H-1III), 4.92 (s, 1 H, H-1II), 4.62 (s, 1 H, H-1I), 4.09 (m,
1 H), 3.98–3.95 (d, 4 H), 3.87–3.72 (m, 14 H), 3.66–
3.48 (m, 18 H), 3.28 (s, 3 H, CH3); 13C NMR (D2O): l
104.82, 104.82, 103.36, 103.26, 103.26 (C-1), 81.22,
81.12, 80.97, 80.91, 76.06, 75.83, 75.29, 74.33, 72.94,
72.58, 72.25, 72.16, 69.66, 69.48, 69.41, 68.67, 63.64,
63.52, 63.44, 57.37 (CH3). MALDI-TOFMS Calcd for
C31H54O26: [M] 842.3, Found: [M+Na] 865.6.
1
(0.45 g, 90%): [h]D20 −25.9° (c 0.9, CHCl3); H NMR
(CDCl3): l 8.07–7.02 (m, 80 H, PhH), 6.02–5.82 (m, 7
H, H-4V, H-4IV, H-4III, H-4II, H-4I, H-3V, H-3IV), 5.75
(dd, 1 H, J1,2 1.8, J2,3 3.0, H-2V), 5.69 (dd, 1 H, J1,2 1.8,
J2,3 3.2 Hz, H-2IV), 5.44–5.41 (m, 1 H, H-3III), 5.33 (s,
2 H, H-1V, H-2III), 5.16 (s, 1 H, H-1IV), 5.02 (s, 1 H,
H-1III), 4.95(d, 1 H, J1,2 1.5 Hz, H-1II), 4.91 (s, 1 H,
H-1I), 4.71–4.66 (m, 1 H), 4.63–4.57 (m, 3 H), 4.54–
4.51 (m, 1 H), 4.49–4.45 (m, 1 H), 4.40 (m, 1 H),
4.33–4.26 (m, 3 H), 4.19–4.00 (m, 8 H), 3.92 (m, 1 H),
3.44 (s, 3 H, CH3O); 13C NMR (CDCl3): l 166.13,
166.05, 166.05, 165.98, 165.91, 165.64, 165.62, 165.38,
165.19, 165.12, 165.01, 164.98, 164.94, 164.94, 164.72,
164.67 (16 Ph), 133.75, 133.57, 133.55, 133.38, 133.34,
133.22, 133.18, 133.09, 133.07, 132.98, 132.88, 132.84,
132.68, 129.99, 129.95, 129.86, 129.84, 129.80, 129.79,
129.76, 129.71, 129.65, 129.61, 129.57, 129.50, 129.30,
129.19, 129.14, 129.07, 129.05, 129.02, 128.98, 128.88,
128.83, 128.61, 128.57, 128.54, 128.51, 128.49, 128.39,
128.35, 128.32, 128.29, 128.27, 128.21, 128.18, 128.06
(16 Ph), 100.48, 100.10, 99.53, 99.35, 98.55 (C-1), 77.24,
76.65 (C-3), 76.11, 75.02, 71.77, 71.50, 71.12, 70.49,
70.02, 69.74, 69.67, 69.47, 69.42, 69.16, 68.70, 68.40,
68.19, 66.64, 66.42, 66.34, 62.96, 62.60, 62.41, 62.25
Acknowledgements
This work was supported by The Chinese Academy
of Sciences (KIP-RCEES9904), by The National Natu-
ral Science Foundation of China (Projects 39970864
and 30070815), and by The Ministry of Science and
Technology.
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