Syntheses of β-(1→6)-branched β-(1→3)-linked D-galactans that exist in the rhizomes of Atractylodes lancea DC

Article abstract of DOI:10.1016/j.carres.2005.05.017

Effective syntheses of galactose hepta-, octa-, nona-, and decasaccharides that exist in the rhizomes of Atractylodes lancea DC were achieved with 2,3,4,6-tetra-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (1), 4-methoxyphenyl 2,3,4-tri-O-benzoyl-β

Full text of DOI:10.1016/j.carres.2005.05.017

Carbohydrate
RESEARCH
Carbohydrate Research 340 (2005) 1949–1962
Syntheses of b-(1!6)-branched b-(1!3)-linked D-galactans that
exist in the rhizomes of Atractylodes lancea DC
Aixiao Lia,b and Fanzuo Konga,*
aResearch Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
bHebei University of Science and Technology, College of Sciences, Shijiazhuang 050018, China
Received 18 March 2005; accepted 28 May 2005
Available online 14 July 2005
Abstract—Effective syntheses of galactose hepta-, octa-, nona-, and decasaccharides that exist in the rhizomes of Atractylodes lancea
DC were achieved with 2,3,4,6-tetra-O-benzoyl-a-D-galactopyranosyl trichloroacetimidate (1), 4-methoxyphenyl 2,3,4-tri-O-ben-
zoyl-b-D-galactopyranoside (2), 6-O-acetyl-2,3,4-tri-O-benzoyl-a-D-galactopyranosyl trichloroacetimidate (5), 4-methoxyphenyl 6-
O-acetyl-2,4-di-O-benzoyl-b-D-galactopyranoside (22), and 4-methoxyphenyl 2,4,6-tri-O-benzoyl-b-D-galactopyranoside (26) as
the key synthons. Coupling of 2 with 1, followed by oxidative cleavage of 1-OMP and subsequent trichloroacetimidate formation
gave the b-(1!6)-linked disaccharide donor 4. Condensation of 2 with 5 and subsequent selective deacetylation by methanolysis
produced the b-(1!6)-linked disaccharide acceptor 7. Reaction of 7 with 4, oxidative cleavage of 1-OMP, and trichloroacetimidate
formation produced the tetrasaccharide donor 9. The penta- (15), the hexa- (17), and the heptasaccharide donor 19 were synthesized
similarly. Meanwhile, treatment of 1 with 22 yielded b-(1!3)-linked disaccharide 23 and a-(1!3)-linked disaccharide 25. Oxidative
cleavage of 1-OMp of 23 followed by trichloroacetimidate formation produced the disaccharide donor 24. Coupling of 26 with 24,
again, gave b-linked 27 and a-linked 29. Selective 6-O-deacetylation of 27 afforded the trisaccharide acceptor 28. TMSOTf-pro-
moted condensation 28 of with the tetra- (9), penta- (15), hexa-(17), and heptasaccharide donor 19, followed by deprotection, gave
the target compounds.
ꢀ 2005 Elsevier Ltd. All rights reserved.
Keywords: Galactose; Arabinogalactan
1. Introduction
expression of the activity of AF-ALR-5IIa-1-1.2 The fol-
lowing structure has been suggested for the galactan side
chains of AF-ALR-5IIa-1-1.
An arabino-3,6-galactan, ALR-5IIa-1-1, which shows
intestinal immune system modulating activity, has been
found in the rhizomes of Atractylodes lancea DC.1 The
analysis of the structure–activity relationships of ALR-
5IIa-1-1 by glycosidase digestions has suggested that
the arabino-3,6-galactan moiety in the nonreducing ter-
minal side of ALR-5IIa-1-1 mainly contributes to
expression of the activity.1 The study also suggested that
Araf side chain-trimmed ALR-5IIa-1-1 (AF-ALR-5IIa-
1-1) still shows the intestinal immune system modulating
activity, and the side-chain oligosaccharides released by
exo-b-D-(1!3)-galactanase digestion are important for
As an ongoing project for study on structure–activity
relationships of arabinogalactans, we have synthesized
2- and 3-a-L-arabinofuranose branched b-(1!6)-linked
galactans.3,4 The synthetic arabinogalactans have been
tested, and a definite structure with strong immunoregu-
lating activity has been established.5a Earlier, syntheses
of structurally diverse arabinogalactans were repor-
ted.5b–j We present herein convergent syntheses of the
galactan fragments that exist in AF-ALR-5IIa-1-1.
2. Results and discussion
Retrosynthetic analysis indicated that synthesis of the
galactans as shown in Figure 1 can be achieved through
*
Corresponding author. Tel.: +86 10 6293 6613; fax: +86 10 6292
3563; e-mail: fzkong@mail.rcees.ac.cn
0008-6215/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2005.05.017

1950
A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
24 again gave an anomeric mixture composed of b-
linked trisaccharide 27 and a-linked trisaccharide 29.
Fortunately, the mixture was well separated giving pure
b-linked isomer. Selective deacetylation7 of 27 by meth-
anolysis gave the trisaccharide acceptor 28.
3)-
-
D
-Gal-(1 3)-
-
D
-Gal-(1 3)- -
6
D
-Gal-(1
β
β
β
-D-Gal-(1[ 6)- D-Gal-(1]
-
n
β
n = 0-4, 6-7
β
Figure 1. Galactan side chains of AF-ALR-5IIa-1-1.
With the tetra-, penta-, hexa-, and heptasaccharide
donors and the trisaccharide acceptor building blocks
at hand, the target hepta-, octa-, nona-, and decasaccha-
rides were readily obtained as shown in Schemes 2 and
3. Thus, coupling 28 with 9, 15, 17, and 19, followed
by deacylation with ammonia in methanol, yielded the
heptasaccharide 31, the octasaccharide 33, the nonasac-
charide 35, and the decasaccharide 37, respectively.
In summary, efficient syntheses of galactans consisting
of a b-(1!3)-linked galactopyranosyl backbone and b-
(1!6)-linked side chains of different size attached at
the C-6 were achieved. The described method can be
used in preparation of a variety of different 3,6-branched
galactans.
three steps: (1) preparation of b-(1!6)-linked side
chains, (2) construction of the b-(1!3)-linked back-
bone, and finally, (3) condensation of the above two
moieties. Schemes 1 and 2 show the syntheses of the side
chains, that is the tetrasaccharide donor 9, the pentasac-
charide donor 15, the hexasaccharide donor 17 and the
heptasaccharide donor 19, and the trisaccharide back-
bone 28. Condensation of the 2,3,4-tri-O-benzoyl-b-D-
galactopyranoside 23b with perbenzoylated galactopyr-
anosyl trichloroacetimidate6 1 afforded the disaccharide
3. Subsequent oxidative cleavage of the 4-methoxyphe-
nyl group and subsequent tricholoroacetimidate forma-
tion gave the b-(1!6)-linked disaccharide donor 4.
Coupling of 2 with 5 gave the disaccharide 6, and subse-
quent deacetylation7 yielded the b-(1!6)-linked disac-
charide acceptor 7. Condensation of 7 with 4, followed
by oxidative cleavage of 1-OMp and trichloroacetimi-
date formation, yielded the b-(1!6)-linked tetrasaccha-
ride donor 9. Meanwhile, coupling of 7 with 6-O-acetyl-
2,3,4-tri-O-benzoyl-a-D-galactopyranosyl trichloroace-
timidate (5)3b followed by deacetylation gave trisaccha-
ride acceptor 11, and condensation of 2 with 4, followed
by oxidative cleavage of 1-OMP and trichloroacetimi-
date formation, yielded the trisaccharide donor 13. Then
coupling 11 with 4, 13, and 9, followed by oxidative
cleavage of 1-OMP and trichloroacetimidate formation,
produced the pentasaccharide donor 15, the hexasaccha-
ride donor 17, and the heptasaccharide donor 19,
respectively.
The b-(1!3)-linked galactose trisaccharide acceptor
28 was obtained with some difficulty mainly caused by
poor stereoselectivity in the coupling reactions. First,
the key synthon, 4-methoxyphenyl 6-O-acetyl-2,4-di-O-
benzoyl-b-D-galactopyranoside (22), was prepared read-
ily from 4-methoxyphenyl tetra-O-acetyl-b-D-galactopy-
ranoside by deacetylation, selective 3-O-allylation via a
dibutyltin complex,8 6-O-tritylation, benzoylation, det-
ritylation, acetylation, and deallylation. However, cou-
pling of 22 with 1 produced a mixture consisting of b-
(1!3)-linked disaccharide 23 and a-(1!3)-linked disac-
charide 25, in spite of the existence of a C-2 ester group
in the donor capable of neighboring group participation.
Similar abnormal coupling with the galactose donor
with a C-2 ester group was reported earlier by our
group.9 Oxidative cleavage of the 1-OMp group of 23,
followed by trichloroacetimidate formation, gave disac-
charide donor 24. Condensation of 4-methoxyphenyl
2,4,6-tri-O-benzoyl-b-D-galactopyranoside (26)10 with
3. Experimental
3.1. General methods
Melting points were determined with a ÔMel-TempÕ
apparatus. Optical rotations were determined at 25 ꢁC
with a digital polarimeter. The NMR spectra were re-
corded in CDCl3 with TMS as the internal standard or
D2O with ethanol as the standard on an ARX at
400 MHz. Mass spectra were recorded on an autospec
mass spectrometer using the ESI mode. Elemental anal-
yses were done on elemental analyzer model 1108 EA.
Thin-layer chromatography (TLC) was performed on
silica gel HF254 with detection by charring with 30%
(v/v) H2SO4 in MeOH or in some cases by a UV detec-
tor. Column chromatography was conducted by elution
of a column (10 · 240 mm, 18 · 300 mm, 35 · 400 mm)
of silica gel (100–200 mesh) with EtOAc–petroleum
ether (60–90 ꢁC) as the eluent. Solutions were concen-
trated at <60 ꢁC under diminished pressure. Dry sol-
vents were distilled over CaH2 and stored over
molecular sieves.
3.2. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranoside (3)
A solution of 2 (2.0 g, 3.3 mmol) and 2,3,4,6-tetra-O-
benzoyl-a-D-galactopyranosyl trichloroacetimidate (1,
3.0 g, 4.0 mmol) in dry CH2Cl2 (80 mL) was stirred.
TMSOTf (30 lL) was added dropwise at ꢀ20 ꢁC with
nitrogen protection. The reaction mixture was stirred
for 2 h, during which time the temperature was gradu-
ally raised to ambient. Then the mixture was neutralized
with triethylamine. Concentration of the reaction mix-

A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
1951
OBz
OBz
BzO
OH
3 R1 = OMp, R2 = H
OBz
BzO
OBz
O
(1) CAN
O
OBz
BzO
O
O
(2) CCl3CN
OMp
4 R1 = H, R2= OC(NH)CCl3
+
BzO
BzO
OBz
O
O
OBz
R1
R2
OCNHCCl3
BzO
2
1
BzO
BzO
OR
OH
OBz
BzO
OBz
OAc
OBz
BzO
6 R = Ac
7 R = H
O
O
1% MeCOCl in
MeOH/CH2Cl2
O
O
OMp
+
BzO
BzO
OBz
BzO
OBz
OCNHCCl3
OMp
2
5
BzO
OBz
OBz
O
O
BzO
8 R1 = OMp, R2 = H
BzO BzO
(1) CAN
4
+
7
O
(2) CCl3CN
9 R1 = H, R2= OC(NH)CCl3
O
BzO
BzO
BzO
O
O
BzO
BzO BzO
O
R1
OR
OBz
BzO
BzO
O
BzO
BzO
R2
O
BzO
BzO
BzO
10 R = Ac
11 R = H
OAc
O
OBz
1% MeCOCl in
MeOH/CH2Cl2
O
O
7
+
BzO
BzO
BzO
OBz
O
OMp
OCNHCCl3
BzO
5
OBz
OBz
BzO
O
O
12 R1 = OMp, R2 = H
BzO
BzO
(1) CAN
O
(2) CCl3CN
13 R1 = H, R2 = OC(NH)CCl3
O
4
+
2
BzO
BzO
BzO
BzO
O
O
R1
OBz
O
BzO
BzO
BzO
R2
BzO
O
BzO
O
14 R1 = OMp, R2 = H
(1) CAN
BzO
BzO
BzO
(2) CCl3CN
O
15 R1 = H, R2= OC(NH)CCl3
4
+
11
O
BzO
BzO
BzO
BzO
O
O
OBz
O
BzO
BzO
OBz
BzO
BzO
O
R1
O
BzO
R2
BzO
BzO
BzO
O
O
BzO
16 R1 = OMp, R2 = H
O
BzO
O
(1) CAN
(2) CCl3CN
11
17 R1 = H, R2 = OC(NH)CCl3
13
BzO
+
BzO
BzO
BzO
O
O
BzO
BzO
O
O
BzO
BzO
BzO
BzO
O
R1
BzO
R2
Scheme 1.
ture, followed by purification on a silica gel column with
3:1 petroleum ether–EtOAc as the eluent, gave 3 (3.4 g,
87%) as a syrup: [a]D +38.6 (c 1.0, CHCl3); H NMR
2H, J 9.1 Hz, CH3OC6H4O–), 6.79 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.01 (d, 1H, J3,4 3.2 Hz, H-40), 5.97
(d, 1H, J3,4 3.2 Hz, H-4), 5.90 (m, 1H, J1,2 8.0 Hz, J2,3
10.4 Hz, H-20), 5.80 (dd, 1H, J2,3 10.4 Hz, J1,2 8.0 Hz,
1
(400 Hz, CDCl3): d 8.10–7.24 (m, 35H, 7PhH), 6.98 (d,

1952
A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
OBz
BzO
BzO
O
O
BzO
BzO
O
O
BzO
BzO
BzO
BzO
O
O
18 R1 = OMp, R2 = H
BzO
BzO
(1) CAN
O
O
(2) CCl3CN
19 R1 = H, R2 = OC(NH)CCl3
11
9
BzO
+
BzO
BzO
O
O
BzO
BzO
BzO
BzO
O
O
BzO
BzO
BzO
O
R1
BzO
R2
OAc
OAc
OH
OBz
AllO
OBz
OBz
AllO
O
PdCl2
O
O
OMp
OMp
OMp
HO
OBz
OBz
22
OBz
21
20
OBz
O
OAc
OBz
OBz
BzO
23 R1 = OMp, R2 = H
O
(1) CAN
R1
O
(2) CCl3CN
24 R1 = H, R2 = OC(NH)CCl3
R2
BzO
BzO
1
+
22
OBz
OAc
O
OBz
OBz
O
OMp
BzO
BzO
BzO
O
25
OBz
O
OR
OBz
O
OBz
OBz
OBz
OBz
27 R = Ac
OBz
1% MeCOCl in
MeOH/CH2Cl2
O
OMp
OMp
O
O
O
28 R = H
BzO
BzO
BzO
BzO
OBz
OBz
HO
O
OBz
O
OAc
O
OBz
O
24
OMp
OBz
BzO
+
OBz
BzO
26
BzO
29
BzO
O
OR
OR
RO
O
O
RO
OR
O
O
RO
RO OR
30 R = OBz
31 R = H
O
NH3-MeOH
O
RO
RO
OR
9
O
+
28
O
RO
OR
RO
OR
OR
O
OR
OR
RO
O
O
OMp
O
O
OR
RO
RO
Scheme 2.
H-2), 5.60–5.55 (m, 2H, H-30, H-3), 5.17 (d, 1H, J1,2
8.0 Hz, H-10), 4.97 (d, 1H, J1,2 8.0 Hz, H-1), 4.44 (dd,
1H, J5,6 6.0 Hz, J6,6 10.4 Hz, H-60), 4.31–4.23 (m, 2H,
H-60, H-50), 4.20 (m, 1H, H-5), 4.16 (dd, 1H, J5,6
4.4 Hz, J6,6 10.8 Hz, H-6), 4.07 (dd, 1H, J5,6 4.8 Hz,
J6,6 11.2 Hz, H-6), 3.71 (s, 3H, CH3O). Anal. Calcd
for C68H56O19: C, 69.38; H, 4.79. Found: C, 69.29; H,
4.83.

A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
1953
OR
O
RO
RO
O
RO
RO
O
O
RO
RO
RO
O
O
RO
32 R = OBz
33 R = H
RO
RO
RO
NH3-MeOH
O
15
+
28
O
OR
RO
O
O
RO
OR
O
RO
OR
OR
OR
OR
RO
O
O
OMp
O
O
OR
O
OR
RO
RO
RO
O
RO
RO
RO
O
O
RO
RO
RO
O
O
RO
OR
RO
O
O
RO
RO
34 R = OBz
35 R = H
RO
RO
NH3-MeOH
O
O
17
+
28
RO
OR
O
O
RO
OR
RO
OR
OR
OR
OR
OR
RO
OR
RO
O
O
O
O
OMp
O
O
O
RO
RO
RO
RO
RO
RO
O
O
RO
RO
RO
O
O
RO
RO
RO
O
O
OR
RO
RO
36 R = OBz
37 R = H
NH3-MeOH
O
O
RO
RO
O
19
+
28
RO
O
RO
OR
OR
O
RO
OR
O
RO
OR
OR
OR
O
O
O
OMp
O
O
RO
RO
RO
RO
Scheme 3.
3.3. 2,3,4,6-Tetra-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-a-D-galactopyranosyl
trichloroacetimidate (4)
7.8 g, 14.2 mmol), and the mixture was stirred at rt for
30 min, at the end of which time TLC (2:1 petroleum
ether–EtOAc) indicated that the reaction was complete.
The mixture was extracted with CH2Cl2 (5 · 50 mL) and
washed with water. The organic layer was concen-
trated, and the crude hemiacetal was purified by column
To a solution of 3 (3.4 g, 2.9 mmol) in 4:1 CH3CN–H2O
(50 mL) was added ceric ammonium nitrate (CAN,

1954
A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
chromatography (2:1 petroleum ether–EtOAc) to afford
a solid. To a solution of the solid in CH2Cl2 (80 mL)
were added trichloroacetonitrile (0.48 mL, 4.8 mmol)
and anhyd K2CO3 (2.2 g, 16 mmol). The reaction mix-
ture was stirred overnight at rt and then filtered, and
the filtrate was concentrated in vacuo. The residue was
purified by column chromatography (2:1 petroleum
ether–EtOAc) to give 4 (2.28 g, 69%, for two steps) as
30H, 6PhH), 6.95 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.74 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 6.01 (d, 1H, J3,4
3.2 Hz, H-40), 5.95 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-20), 5.81 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2),
5.76 (d, 1H, J3,4 3.2 Hz, H-4), 5.58 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-30), 5.52 (dd, 1H, J3,4 3.2 Hz,
J2,3 10.4 Hz, H-3), 5.15 (d, 1H, J1,2 8.0 Hz, H-10), 4.90
(d, 1H, J1,2 8.0 Hz, H-1), 4.27 (m, 1H, H-50), 4.10 (dd,
1H, J5,6 5.4 Hz, J6,6 11.2 Hz, H-6), 4.01 (dd, 1H, J5,6
5.4 Hz, J6,6 11.2 Hz, H-6), 3.91 (m, 1H, H-5), 3.66 (dd,
1H, J5,6 6.4 Hz, J6,6 12 Hz, H-60), 3.48 (dd, 1H, J5,6
5.6 Hz, J6,6 12 Hz, H-60), 3.69 (s, 3H, CH3O). Anal.
Calcd for C61H52O18: C, 68.28; H, 4.88. Found: C,
67.13; H, 4.70.
1
a syrup: [a]D +57.1 (c 1.0, CHCl3); H NMR (400 Hz,
CDCl3): d 8.70 (s, 1H, CNHCCl3), 8.32–7.25 (m, 35H,
7PhH), 6.75 (d, 1H, J1,2 3.6 Hz, a H-1), 6.10 (d, 1H,
J3,4 3.2 Hz, H-40), 6.02 (dd, 1H, J1,2 3.6, J2,3 10.4 Hz,
H-20), 5.92 (d, 1H, J3,4 3.4 Hz, H-4), 5.86 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-30), 5.74 (dd, 1H, J1,2 8.0 Hz,
J2,3 10.4 Hz, H-2), 5.53 (dd, 1H, J3,4 3.4 Hz, J2,3
10.4 Hz, H-3), 4.90 (d, 1H, J1,2 8.0 Hz, b H-10), 4.38
(dd, 1H, J5,6 4.8 Hz, J6,6 10.8 Hz, H-60), 4.26 (dd, 1H,
J5,6 5.4 Hz, J6,6 11.2 Hz, H-60), 4.21–4.15 (m, 3H, H-
50, H-5, H-6), 3.89 (dd, 1H, J5,6 5.4 Hz, J6,6 11.2 Hz,
H-6). Anal. Calcd for C63H50Cl3NO18: C, 62.25; H,
4.11. Found: C, 62.39; H, 4.25.
3.6. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranoside (8)
Compounds
4 (1.36 g, 1.12 mmol) and 7 (1.0 g,
3.4. 4-Methoxyphenyl 6-O-acetyl-2,3,4-tri-O-benzoyl-
b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranoside (6)
0.93 mmol) in dry CH2Cl2 (80 mL) were coupled by
the same procedure as described in the preparation of
3 to give tetrasaccharides 8 as a syrup (1.56 g, 79%):
[a]D +49.2 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3):
d 8.09–7.19 (m, 65H, 13PhH), 6.94 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.76 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
5.95–5.91 (m, 3H, H-2000, H-4000, H-400), 5.89 (d, 1H, J3,4
3.6 Hz, H-40), 5.86 (d, 1H, J3,4 3.6 Hz, H-4), 5.67 (dd,
1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-200), 5.62 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-20), 5.58–5.54 (m, 3H, H-2, H-
3000, H-300), 5.53 (dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-
30), 5.43 (dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 5.13
(d, 1H, J1,2 8.0 Hz, H-1000), 4.82 (d, 1H, J1,2 8.0 Hz, H-
100), 4.56 (d, 1H, J1,2 8.0 Hz, H-10), 4.48 (d, 1H, J1,2
8.0 Hz, H-1), 4.24–4.20 (m, 2H, H-6000, H-6000), 4.12 (m,
1H, H-5000), 4.10–4.05 (m, 4H, H-600, H-600, H-500, H-60),
4.03 (dd, 1H, J5,6 5.4 Hz, J6,6 10.8 Hz, H-60), 3.92 (m,
1H, H-50), 3.76 (m, 1H, H-5), 3.68 (s, 3H, OCH3), 3.51
(dd, 1H, J5,6 5.6 Hz, J6,6 10.8 Hz, H-6), 3.42 (dd, 1H,
J5,6 6.6 Hz, J6,6 12 Hz, H-6); 13C NMR (CDCl3,
100 MHz): d 166.1, 165.8, 165.6, 165.6, 165.4, 165.4,
165.4, 165.3, 165.3, 165.2, 165.2, 165.0, 165.0 (13C,
13COPh), 101.0, 100.9, 100.9, 100.8 (4C, C-1). Anal.
Calcd for C122H100O35: C, 68.92; H, 4.74. Found: C,
68.73; H, 4.86.
Compounds 5 (2.0 g, 2.0 mmol) and 4-methoxyphenyl
2,3,4-tri-O-benzoyl-b-D-galactopyranoside (2, 1.5 g,
2.5 mmol) in dry CH2Cl2 (50 mL) were coupled by the
same procedure as described in the preparation of 3 to
give disaccharides 6 as a syrup (2.32 g, 81%): [a]D +31.4
1
(c 1.0, CHCl3); H NMR (400 Hz, CDCl3): d 8.07–7.23
(m, 30H, 6PhH), 6.95 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.77 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 6.00 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-20), 5.96 (d, 1H, J3,4 3.2 Hz, H-
40), 5.84 (d, 1H, J3,4 3.2 Hz, H-4), 5.77 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.59 (dd, 1H, J3,4 3.2 Hz, J2,3
10.4 Hz, H-30), 5.52 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz,
H-3), 5.15 (d, 1H, J1,2 8.0 Hz, H-10), 4.92 (d, 1H, J1,2
8.0 Hz, H-1), 4.31 (dd, 1H, J5,6 5.4 Hz, J6,6 11.2 Hz,
H-60), 4.15–4.11 (m, 4H, H-60, H-50, H-5, H-6), 4.02
(dd, 1H, J5,6 5.4 Hz, J6,6 11.2 Hz, H-6), 3.69 (s, 3H,
CH3O), 1.98 (s, 3H, CH3CO). Anal. Calcd for
C63H54O19: C, 67.85; H, 4.88. Found: C, 67.93; H, 4.74.
3.5. 4-Methoxyphenyl 2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranoside (7)
3.7. 2,3,4,6-tetra-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-a-D-galactopyranosyl
trichloroacetimidate (9)
To a solution of 6 (2.32 g, 2.07 mmol) in 1:1 CH3OH–
CH2Cl2 (100 mL) was added CH3COCl (1 mL), and
the reaction was carried out at rt for 48 h. Disaccharide
7 (1.87 g, 83%) was obtained as a syrup after purifying
the product by column chromatography with 2:1 petro-
leum ether–EtOAc as the eluent: [a]D +19.2 (c 1.0,
CHCl3); 1H NMR (400 Hz, CDCl3): d 8.11–7.23 (m,
To a solution of 8 (1.56 g, 0.73 mmol) in 4:1 CH3CN–
H2O (20 mL) was added CAN (2.0 g, 3.7 mmol), and

A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
1955
the mixture was treated by the same procedure as de-
scribed in the preparation of 4 to give 9 as a syrup
(1.03 g, 65%, for two steps): [a]D +81.2 (c 1.0, CHCl3);
1H NMR (400 Hz, CDCl3): d 8.30 (s, 1H, NH), 8.02–
7.21 (m, 65H, 13PhH), 6.72 (d, 1H, J1,2 3.6 Hz, a H-
1), 6.03 (d, 1H, J3,4 3.6 Hz, H-4000), 5.98 (dd, 1H, J1,2
3.6 Hz, J2,3 10.4 Hz, H-2000), 5.87–5.84 (m, 3H, H-400,
H-40, H-4), 5.78 (dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-
3000), 5.61 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-200), 5.57
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20), 5.50 (dd, 1H,
J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.47 (dd, 1H, J2,3
10.4 Hz, J3,4 3.6 Hz, H-300), 5.44 (dd, 1H, J2,3 10.4 Hz,
J3,4 3.6 Hz, H-30), 5.41 (dd, 1H, J2,3 10.4 Hz, J3,4
3.6 Hz, H-3), 4.80 (d, 1H, J1,2 8.0 Hz, H-1000), 4.51 (d,
1H, J1,2 8.0 Hz, H-100), 4.42 (d, 1H, J1,2 8.0 Hz, H-10),
4.16 (dd, 1H, J5,6 6.0 Hz, J6,6 11.2 Hz, H-6000), 4.14–
4.03 (m, 3H, H-6000, H-600, H-600, H-60), 4.01 (dd, 1H,
J5,6 5.6 Hz, J6,6 11.4 Hz, H-60), 3.95 (m, 1H, H-5000),
3.79–3.70 (m, 3H, H-500, H-50, H-5), 3.41 (dd, 1H, J5,6
5.6 Hz, J6,6 10.8 Hz, H-6), 3.30 (dd, 1H, J5,6 6.6 Hz,
J6,6 12 Hz, H-6); 13C NMR (CDCl3, 100 MHz): d
166.1, 166.0, 165.9, 165.8, 165.7, 165.5, 165.5, 165.4,
165.3, 165.2, 165.2, 165.1, 165.0 (13C, 13COPh), 101.5,
101.4, 101.0, 100.7 (4C, C-1). Anal. Calcd for
3.9. 4-Methoxyphenyl 2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranoside (11)
To a solution of 10 (6.0 g, 3.78 mmol) in 1:1 CH3OH–
CH2Cl2 (100 mL) was added CH3COCl (1 mL), and
the reaction was carried out by the same procedure as
described in the preparation of 7 to give 11 as a syrup
(5.0 g, 85%): [a]D +43.6 (c 2.0, CHCl3); 1H NMR
(400 MHz, CDCl3): d 8.05–7.23 (m, 45H, 9PhH), 6.94
(d, 2H, J 9.1 Hz, CH3OC6H4O–), 6.76 (d, 2H, J
9.1 Hz, CH3OC6H4O–), 5.97–5.92 (m, 3H, H-400, H-200,
H-40), 5.73 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20),
5.71 (d, 1H, J3,4 3.6 Hz, H-4), 5.66 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.58 (dd, 1H, J2,3 10.4 Hz,
J3,4 3.2 Hz, H-300), 5.51 (dd, 1H, J2,3 10.4 Hz, J3,4
3.6 Hz, H-30), 5.46 (dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz,
H-3), 5.16 (d, 1H, J1,2 8.0 Hz, H-100), 4.81 (d, 1H, J1,2
8.0 Hz, H-10), 4.56 (d, 1H, J1,2 8.0 Hz, H-1), 4.26 (m,
1H, H-500), 4.11 (dd, 1H, J5,6 5.2 Hz, J6,6 10.4 Hz, H-
60), 4.07 (m, 1H, H-50), 4.00 (dd, 1H, J5,6 6.8 Hz, J6,6
10.4 Hz, H-60), 3.90–3.84 (m, 2H, H-6, H-5), 3.65 (s,
3H, OCH3), 3.60 (dd, 1H, J5,6 5.2 Hz, J6,6 10 Hz, H-6),
3.50 (dd, 1H, J5,6 6.8 Hz, J6,6 12 Hz, H-6), 3.35 (dd,
1H, J5,6 6.0 Hz, J6,6 12 Hz, H-6); 13C NMR (CDCl3,
100 MHz): d 166.2, 165.8, 165.7, 165.6, 165.4, 165.3,
165.2, 165.2, 165.0 (9C, 9COPh), 101.5, 101.1, 100.8
(3C, C-1). Anal. Calcd for C88H74O26: C, 68.30; H,
4.82. Found: C, 68.41; H, 4.69.
C117H94Cl3NO34: C, 64.92; H, 4.38. Found: C, 64.78;
H, 4.25.
3.8. 4-Methoxyphenyl 6-O-acetyl-2,3,4-tri-O-benzoyl-
b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranoside (10)
3.10. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranoside (12)
Compounds
7
(5.0 g, 4.66 mmol) and
5
(3.8 g,
5.59 mmol) in dry CH2Cl2 (60 mL) were coupled by the
same procedure as described in the preparation of 3 to
give trisaccharide 10 as a syrup (6.0 g, 89%): [a]D +51.2
1
(c 2.0, CHCl3); H NMR (400 MHz, CDCl3): d 8.07–
Compounds 4 (3.0 g, 2.47 mmol) and 2 (1.23 g,
7.18 (m, 45H, 9PhH), 6.90 (d, 2H, J 9.1 Hz, CH3O-
C6H4O–), 6.73 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 5.97
(d, 1H, J3,4 3.6 Hz, H-400), 5.95–5.92 (m, 2H, H-200, H-
40), 5.79 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20), 5.71
(d, 1H, J3,4 3.6 Hz, H-4), 5.68 (dd, 1H, J1,2 8.0 Hz, J2,3
10.4 Hz, H-2), 5.56 (dd, 1H, J2,3 10.4 Hz, J3,4 3.2 Hz,
H-300), 5.52–5.45 (m, 2H, H-30, H-3), 5.13 (d, 1H, J1,2
8.0 Hz, H-100), 4.79 (d, 1H, J1,2 8.0 Hz, H-10), 4.61 (d,
1H, J1,2 8.0 Hz, H-1), 4.41 (dd, 1H, J5,6 5.4 Hz, J6,6
11.2 Hz, H-600), 4.34 (dd, 1H, J5,6 5.4 Hz, J6,6 11.2 Hz,
H-600), 4.24 (m, 1H, H-500), 4.10 (dd, 1H, J5,6 5.2 Hz,
J6,6 10.4 Hz, H-60), 4.05 (m, 1H, H-50), 3.95 (dd, 1H,
J5,6 6.8 Hz, J6,6 10.4 Hz, H-60), 3.89–3.82 (m, 2H, H-6,
H-5), 3.65 (s, 3H, OCH3), 3.60 (dd, 1H, J5,6 5.2 Hz, J6,6
10 Hz, H-6), 1.96 (s, 3H, CH3CO); 13C NMR (CDCl3,
100 MHz): d 170.1 (1C, CH3CO), 166.2, 166.1, 165.7,
165.7, 165.6, 165.5, 165.4, 165.2, 165.1 (9C, 9COPh),
101.6, 101.2, 100.9 (3C, C-1). Anal. Calcd for
C90H76O27: C, 68.00; H, 4.82. Found: C, 68.16; H, 4.87.
2.05 mmol) in dry CH2Cl2 (50 mL) were coupled by
the same procedure as described in the preparation of
3 to give trisaccharide 12 (3.14 g, 85%) as a syrup: [a]D
+68.4 (c 1.0, CHCl3); 1H NMR (400 Hz, CDCl3): d
8.07–7.24 (m, 50H, 10PhH), 6.93 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.76 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
5.97–5.93 (m, 2H, H-400, H-200), 5.89 (d, 1H, J3,4
3.2 Hz, H-40), 5.87 (d, 1H, J3,4 3.2 Hz, H-4), 5.72 (dd,
1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20), 5.68 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.59 (dd, 1H, J3,4 3.2 Hz,
J2,3 10.4 Hz, H-300), 5.55 (dd, 1H, J3,4 3.2 Hz, J2,3
10.4 Hz, H-30), 5.48 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz,
H-3), 5.17 (d, 1H, J1,2 8.0 Hz, H-100), 4.79 (d, 1H, J1,2
8.0 Hz, H-10), 4.63 (d, 1H, J1,2 8.0 Hz, H-1), 4.30 (dd,
1H, J5,6 5.6 Hz, J6,6 12 Hz, H-600), 4.25 (m, 1H, H-500),
4.16–4.11 (m, 2H, H-600, H-60), 4.09–4.04 (m, 2H, H-50,
H-5), 3.97 (dd, 1H, J5,6 6.4 Hz, J6,6 10 Hz, H-60), 3.88
(dd, 1H, J5,6 6.0 Hz, J6,6 10.4 Hz, H-6), 3.68 (s, 3H,
CH3O), 3.60 (dd, 1H, J5,6 6.0 Hz, J6,6 10 Hz, H-6); 13C

1956
A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
NMR (CDCl3, 100 MHz): d 166.2, 166.0, 165.9, 165.7,
165.5, 165.4, 165.3, 165.3, 165.2, 165.1 (10C, 10COPh),
101.3, 101.1, 100.7 (3C, C-1). Anal. Calcd for
C95H78O27: C, 69.08; H, 4.76. Found: C, 69.29; H, 4.92.
H-1), 4.49 (d, 1H, J1,2 8.0 Hz, H-1), 4.42 (d, 1H, J1,2
8.0 Hz, H-1), 3.71 (s, 3H, CH3O); 13C NMR (100 MHz,
CDCl3): d 166.9, 166.7, 166.7, 166.4, 166.3, 166.2, 166.1,
165.9, 165.5, 165.4, 165.3, 165.2, 165.2, 165.1, 165.1,
165.0 (16C, 16COPh), 101.7, 101.4, 101.2, 100.7, 100.6
(5C, C-1). Anal. Calcd for C149H122O43: C, 68.81; H,
4.73. Found: C, 68.99; H, 4.91.
3.11. 2,3,4,6-Tetra-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-
2,3,4-tri-O-benzoyl-a-D-galactopyranosyl trichloro-
acetimidate (13)
3.13. 2,3,4,6-Tetra-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-
2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-2,3,4-tri-O-
benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-
a-D-galactopyranosyl trichloroacetimidate (15)
To a solution of 12 (3.0 g, 1.81 mmol) in 4:1 CH3CN–
H2O (50 mL) was added CAN (4.0 g, 7.27 mmol), and
the mixture was treated by the same procedure as
described in the preparation of 4 to give trisaccharide
donor 13 (2.2 g, 71% for two steps) as a syrup: [a]D
+79.1 (c 1.0, CHCl3); 1H NMR (400 Hz, CDCl3): d
8.33 (s, 1H, NH), 7.93–7.22 (m, 50H, 10PhH), 6.74 (d,
1H, J1,2 3.6 Hz, a H-1), 6.05 (d, 1H, J3,4 3.2 Hz, H-400),
5.99 (dd, 1H, J1,2 3.6 Hz, J2,3 10.4 Hz, H-200), 5.89–5.87
(m, 2H, H-40, H-4), 5.81 (dd, 1H, J3,4 3.2 Hz, J2,3
10.4 Hz, H-300), 5.67 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-20), 5.62 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2),
5.53 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-30), 5.44 (dd,
1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 4.73 (d, 1H, J1,2
8.0 Hz, H-10), 4.59 (d, 1H, J1,2 8.0 Hz, H-1), 4.23 (dd,
1H, J5,6 6.0 Hz, J6,6 10.8 Hz, H-600), 4.12 (m, 1H, H-
500), 4.09–4.00 (m, 4H, H-600, H-60, H-50, H-5), 3.89
(dd, 1H, J5,6 6.8 Hz, J6,6 10 Hz, H-60), 3.76 (dd, 1H,
J5,6 6.4 Hz, J6,6 10.4 Hz, H-6), 3.68 (s, 3H, CH3O),
3.51 (dd, 1H, J5,6 6.0 Hz, J6,6 10 Hz, H-6); 13C NMR
(CDCl3, 100 MHz): d 166.9, 166.5, 166.2, 166.1, 165.9,
165.8, 165.7, 165.5, 165.3, 165.1 (10C, 10COPh), 101.7,
101.4, 100.9 (3C, C-1). Anal. Calcd for C90H72Cl3NO26:
C, 63.96; H, 4.29. Found: C, 53.71; H, 4.42.
To a solution of 14 (1.5 g, 0.58 mmol) in 4:1 CH3CN–
H2O (50 mL) was added CAN (1.58 g, 2.88 mmol), and
the mixture was treated by the same procedure as de-
scribed in the preparation of 4 to give pentasaccharide
donor 15 (958 mg, 63% for two steps) as a syrup: [a]D
+59.3 (c 1.0, CHCl3); 1H NMR (400 Hz, CDCl3): d
8.37 (s, 1H, NH), 8.11–7.21 (m, 80H, 16PhH), 6.77 (d,
1H, J1,2 3.6 Hz, a H-1), 6.05 (d, 1H, J3,4 3.6 Hz, H-4),
6.00 (dd, 1H, J1,2 3.6 Hz, J2,3 10.4 Hz, H-2), 5.89–5.87
(m, 3H, 3H-4), 5.83 (d, 1H, J3,4 3.6 Hz, H-4), 5.78 (dd,
1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 5.70 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.66 (dd, 1H, J1,2 8.0 Hz,
J2,3 10.4 Hz, H-2), 5.59 (dd, 1H, J1,2 8.0 Hz, J2,3
10.4 Hz, H-2), 5.50–5.47 (m, 3H, H-2, 2H-3), 5.44 (dd,
1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 5.39 (dd, 1H, J2,3
10.4 Hz, J3,4 3.6 Hz, H-3), 4.81 (d, 1H, J1,2 8.0 Hz, H-
1), 4.55 (d, 1H, J1,2 8.0 Hz, H-1), 4.51 (d, 1H, J1,2
8.0 Hz, H-1), 4.41 (d, 1H, J1,2 8.0 Hz, H-1); 13C NMR
(CDCl3, 100 MHz): d 166.1, 166.0, 165.9, 165.8, 165.8,
165.7, 165.5, 165.5, 165.4, 165.4, 165.3, 165.2, 165.2,
165.1, 165.0, 164.9 (16C, 16COPh), 101.7, 101.4, 101.1,
3.12. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranoside (14)
101.0, 100.6 (5C, C-1). Anal. Calcd for C144H116
Cl3NO42: C, 65.54; H, 4.43. Found: C, 65.32; H, 4.28.
-
3.14. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-
tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-
benzoyl-b-D-galactopyranoside (16)
Compounds 4 (1.5 g, 1.23 mmol) and 11 (1.58 g,
1.02 mmol) in dry CH2Cl2 (50 mL) were coupled by the
same procedure as described in the preparation of 3 to
give pentasaccharide 14 (2.14 g, 81%) as a syrup: [a]D
+22.3 (c 1.0, CHCl3); 1H NMR (400 Hz, CDCl3): d
7.93–7.21 (m, 80H, 16PhH), 6.88 (d, 2H, J 9.1 Hz, CH3O-
C6H4O–), 6.74 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 5.91 (dd,
1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.90–5.87 (m, 3H, 3H-
4), 5.86 (d, 1H, J3,4 3.2 Hz, H-4), 5.84 (d, 1H, J3,4 3.2 Hz,
H-4), 5.66 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.62
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.58–5.55 (m,
3H, 2H-2, H-3), 5.53 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz,
H-3), 5.46–5.43 (m, 2H, 2H-3), 5.41 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-3), 5.10 (d, 1H, J1,2 8.0 Hz, H-1),
4.80 (d, 1H, J1,2 8.0 Hz, H-1), 4.53 (d, 1H, J1,2 8.0 Hz,
Coupling of 11 (1.0 g, 0.65 mmol) with 13 (1.31 g,
0.78 mmol) under the same conditions as described for
the coupling of 1 with 2 gave hexasaccharide 16
(1.58 g, 80%) as a syrup: [a]D +39.5 (c 1.0, CHCl3);
1H NMR (400 MHz, CDCl3): d 7.94–7.22 (m, 95H,
19PhH), 6.77 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 6.73
(d, 2H, J 9.1 Hz, CH3OC6H4O–), 5.95–5.90 (m, 2H,
H-2, H-4), 5.89 (d, 1H, J3,4 3.4 Hz, H-4), 5.87 (d, 1H,
J3,4 3.4 Hz, H-4), 5.85–5.80 (m, 4H, H-2, 3H-4), 5.65
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.62 (dd, 1H,
J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.59 (dd, 1H, J1,2

A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
1957
8.0 Hz, J2,3 10.4 Hz, H-2), 5.56–5.55 (m, 3H, H-2, 2H-3),
5.51 (dd, 1H, J3,4 3.4 Hz, J2,3 10.4 Hz, H-3), 5.47–5.45
(m, 2H, 2H-3), 5.40 (dd, 1H, J3,4 3.4 Hz, J2,3 10.4 Hz,
H-3), 5.11 (d, 1H, J1,2 8.0 Hz, H-1), 4.83 (d, 1H, J1,2
8.0 Hz, H-1), 4.54 (d, 1H, J1,2 8.0 Hz, H-1), 4.50 (d,
1H, J1,2 8.0 Hz, H-1), 4.46 (d, 1H, J1,2 8.0 Hz, H-1),
4.37 (d, 1H, J1,2 8.0 Hz, H-1), 3.69 (s, 3H, CH3O); 13C
NMR (100 MHz, CDCl3): d 167.3, 167.2, 167.0. 166.9,
166.7, 166.7, 166.6, 166.2, 166.1, 166.0, 165.9, 165.6,
165.5, 165.4, 165.3, 165.2, 165.2, 165.1, 165.0 (19C,
19COPh), 101.6, 101.5, 101.4, 101.2, 101.0, 100.9 (6C,
C-1). Anal. Calcd for C176H144O51: C, 68.74; H, 4.72.
Found: C, 68.51; H, 4.89.
the same procedure as described in the preparation of
3 to give heptasaccharide 18 as a syrup (2.4 g, 75%):
[a]D +67.2 (c 1.0, CHCl3); H NMR (400 Hz, CDCl3):
1
d 8.13–7.20 (m, 110H, 22PhH), 6.91 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.73 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.01 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.97–5.96
(m, 2H, 2H-4), 5.90 (d, 1H, J3,4 3.4 Hz, H-4), 5.87 (d,
1H, J3,4 3.4 Hz, H-4), 5.85–5.78 (m, 4H, H-2, 3H-4),
5.66 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.62 (dd,
1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.60–5.55 (m, 4H,
2H-2, 2H-3), 5.53 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-2), 5.51 (dd, 1H, J3,4 3.4 Hz, J2,3 10.4 Hz, H-3),
5.48–5.43 (m, 3H, 3H-3), 5.37 (dd, 1H, J3,4 3.4 Hz, J2,3
10.4 Hz, H-3), 5.13 (d, 1H, J1,2 8.0 Hz, H-1), 4.85 (d,
1H, J1,2 8.0 Hz, H-1), 4.60–4.56 (m, 2H, 2H-1), 4.51
(d, 1H, J1,2 8.0 Hz, H-1), 4.47 (d, 1H, J1,2 8.0 Hz, H-
1), 4.39 (d, 1H, J1,2 8.0 Hz, H-1), 3.69 (s, 3H, CH3O);
13C NMR (CDCl3, 100 MHz): d 167.2, 167.1, 166.9,
166.8, 166.3, 166.2, 166.0, 166.0, 165.9, 165.8, 165.7,
165.6, 165.6, 165.5, 165.4, 165.4, 165.3, 165.2, 165.2,
165.1, 165.0, 165.0 (22C, 22COPh), 101.5, 101.2, 101.1,
100.9, 100.7, 100.6, 100.4 (7C, C-1). Anal. Calcd for
3.15. 2,3,4,6-Tetra-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-
2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-2,3,4-tri-O-
benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-
b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-a-D-
galactopyranosyl trichloroacetimidate (17)
To a solution of 16 (1.5 g, 0.49 mmol) in 4:1 CH3CN–
H2O (50 mL) was added CAN (1.33 g, 2.44 mmol),
and the mixture was treated by the same procedure as
described in the preparation of 4 to give hexasaccharide
donor 17 (970 mg, 64% for two steps) as a syrup: [a]D
C203H166O59: C, 68.69; H, 4.71. Found: C, 67.87; H,
4.65.
3.17. 2,3,4,6-Tetra-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-
2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-2,3,4-tri-O-
benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-
b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-a-D-galacto-
pyranosyl trichloroacetimidate (19)
1
+31.6 (c 1.0, CHCl3); H NMR (400 MHz, CDCl3): d
8.32 (s, 1H, NH), 8.03–7.23 (m, 95H, 19PhH), 6.74 (d,
1H, J1,2 3.6 Hz, a H-1), 6.02 (d, 1H, J3,4 3.6 Hz, H-4),
5.98 (dd, 1H, J1,2 3.6 Hz, J2,3 10.4 Hz, H-2), 5.87 (d,
1H, J3,4 3.6 Hz, H-4), 5.86–5.83 (m, 4H, 4H-4), 5.75
(dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 5.71 (dd, 1H,
J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.65 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.60–5.55 (m, 4H, 2H-2,
2 H-3), 5.51 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2),
5.44 (dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 5.41–5.37
(m, 2H, 2H-3), 4.83 (d, 1H, J1,2 8.0 Hz, H-1), 4.55 (d,
1H, J1,2 8.0 Hz, H-1), 4.50 (d, 1H, J1,2 8.0 Hz, H-1),
4.44 (d, 1H, J1,2 8.0 Hz, H-1), 4.39 (d, 1H, J1,2 8.0 Hz,
H-1); 13C NMR (CDCl3, 100 MHz): d 166.6, 166.5,
166.2, 166.1, 166.1, 165.9, 165.8, 165.7, 165.7, 165.6,
165.5, 165.4, 165.4, 165.3, 165.2, 165.2, 165.1, 165.0,
165.0 (19C, 19COPh), 101.5, 101.3, 101.2, 101.0, 100.9,
100.8 (6C, C-1). Anal. Calcd for C171H138Cl3NO50: C,
65.97; H, 4.47. Found: C, 65.79; H, 4.66.
To a solution of 18 (2.0 g, 0.56 mmol) in 4:1 CH3CN–
H2O (50 mL) was added CAN (1.54 g, 2.82 mmol),
and the mixture was treated by the same procedure as
described in the preparation of 4 to give heptasaccharide
donor 19 (1.23 g, 61% for two steps) as a syrup: [a]D
+47.4 (c 1.0, CHCl3); 1H NMR (400 Hz, CDCl3): d
8.29 (s, 1H, NH), 7.91–7.23 (m, 110H, 22PhH), 6.75
(d, 1H, J1,2 3.2 Hz, a H-1), 6.04 (d, 1H, J3,4 3.6 Hz, H-
4), 6.00 (dd, 1H, J1,2 3.2 Hz, J2,3 10.4 Hz, H-2), 5.84
(d, 1H, J3,4 3.6 Hz, H-4), 5.83–5.81 (m, 4H), 5.79 (dd,
1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 5.75 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.71 (dd, 1H, J1,2 8.0 Hz,
J2,3 10.4 Hz, H-2), 5.65 (dd, 1H, J1,2 8.0 Hz, J2,3
10.4 Hz, H-2), 5.61–5.50 (m, 5H), 5.46 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.43 (dd, 1H, J2,3 10.4 Hz,
J3,4 3.6 Hz, H-3), 5.40–5.37 (m, 3H, H-3), 4.80 (d, 1H,
J1,2 8.0 Hz, H-1), 4.57 (d, 1H, J1,2 8.0 Hz, H-1), 4.47
(d, 1H, J1,2 8.0 Hz, H-1), 4.44–4.40 (m, 2H, H-1), 4.32
(d, 1H, J1,2 8.0 Hz, H-1); 13C NMR (CDCl3,
100 MHz): d 167.0, 166.9, 166.8, 166.6, 166.6, 166.5,
166.4, 166.2, 166.2, 166.1, 165.9, 165.8, 165.7, 165.6,
165.5, 165.4, 165.4, 165.3, 165.2, 165.1, 165.1, 165.0
(22C, 22COPh), 101.8, 101.5, 101.3, 101.0, 100.9,
3.16. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-
tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-tri-O-
benzoyl-b-D- galactopyranosyl-(1!6)-2,3,4-tri-O-
benzoyl-b-D-galactopyranoside (18)
Compounds 11 (1.50 g, 0.97 mmol) and 9 (2.51 g,
1.16 mmol) in dry CH2Cl2 (50 mL) were coupled by

1958
A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
100.9,
C
H, 4.62.
100.6
198H160Cl3NO58: C, 66.28; H, 4.49. Found: C, 66.53;
(7C,
C-1).
Anal.
Calcd
for
4.88. Found: C, 67.76; H, 4.79; 25: [a]D +89.4 (c 2.0,
CHCl3); H NMR (400 MHz, CDCl3): d 8.13–7.09 (m,
1
30H, 6PhH), 6.87 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.69 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 5.92 (d, 1H, J3,4
3.2 Hz, H-40), 5.88 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-20), 5.80 (d, 1H, J3,4 3.2 Hz, H-4), 5.74 (d, 1H, J1,2
3.6 Hz, H-10), 5.61 (dd, 1H, J1,2 3.6 Hz, J2,3 10.4 Hz,
H-2), 5.43 (dd, 1H, J2,3 10.4 Hz, J3,4 3.6 Hz, H-3), 4.87
(d, 1H, J1,2 8.0 Hz, H-1), 4.69 (dd, 1H, J5,6 6.0 Hz, J6,6
10.8 Hz, H-60), 4.31–4.27 (m, 2H, H-60, H-50), 4.25
(dd, 1H, J2,3 10.4 Hz, J3,4 3.2 Hz, H-3), 4.22–4.19 (m,
2H, H-6, H-5), 4.03 (dd, 1H, J5,6 4.8 Hz, J6,6 10.8 Hz,
H-6), 3.65 (s, 3H, OCH3), 1.98 (s, 3H, CH3CO). Anal.
Calcd for C63H54O19: C, 67.85; H, 4.88. Found: C,
67.67; H, 4.71.
3.18. 4-Methoxyphenyl 6-O-acetyl-2,4-di-O-benzoyl-
b-D-galactopyranoside (22)
To a solution of 204 (5.0 g, 9.3 mmol) in pyridine
(20 mL) was added Ac2O (3 mL, 31.8 mmol), the reac-
tion mixture was stirred for 6 h, at the end of which time
the TLC (4:1 petroleum ether–EtOAc) indicated that the
reaction was complete. The mixture was concentrated to
dryness and then purified by column chromatography
with 3:1 petroleum ether–EtOAc as the eluent to afford
21 (5.0 g, 92%). To a solution of 21 (5.0 g, 8.7 mmol) in
anhyd CH3OH (70 mL) was added PdCl2 (200 mg), and
the mixture was stirred at rt for 5 h, at the end of which
time TLC (2:1 petroleum ether–EtOAc) indicated that
the reaction was complete. The mixture was filtered,
and the filtrate was concentrated. The residue was
passed through a silica gel column with 3:1 petroleum
ether–EtOAc as the eluent to give 22 as a syrup (4.0 g,
88%): [a]D +29.5 (c 1.0, CHCl3); 1H NMR (400 Hz,
CDCl3): d 8.16–7.25 (m, 10H, 2PhH), 6.97 (d, 2H, J
9.1 Hz, CH3OC6H4O–), 6.81 (d, 2H, J 9.1 Hz, CH3O-
C6H4O–), 5.71 (d, 1H, J3,4 3.6 Hz, H-4), 5.56 (dd, 1H,
J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.13 (d, 1H, J1,2 8 Hz,
H-1), 4.33–4.26 (m, 2 H, 2H-6). 4.13 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-3), 3.76 (s, 3H, CH3O), 2.01 (s,
3H, CH3CO). Anal. Calcd for C29H28O10: C, 64.92; H,
5.26. Found: C, 64.79; H, 5.21.
3.20. 2,3,4,6-Tetra-O-benzoyl-b-D-galactopyranosyl-
(1!3)-6-O-acetyl-2,4-di-O-benzoyl-a-D-galacto-
pyranosyl trichloroacetimidate (24)
To a solution of 23 (2.74 g, 2.46 mmol) in 4:1 CH3CN–
H2O (50 mL) was added CAN (6.0 g, 12 mmol), and the
mixture was treated by the same procedure as described
in the preparation of 4 to give 24 as a syrup (1.89 g, 67%
for two steps): [a]D +39.2 (c 2.0, CHCl3); 1H NMR
(400 MHz, CDCl3): d 8.65 (s, 1H, NH), 8.18–7.11 (m,
30H, 6PhH), 6.71 (d, 1H, J1,2 3.6 Hz, a H-1), 6.02 (dd,
1H, J1,2 3.6 Hz, J2,3 10.4 Hz, H-20), 5.94 (d, 1H, J3,4
3.2 Hz, H-40), 5.81 (d, 1H, J3,4 3.2 Hz, H-4), 5.74 (dd,
1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.41 (dd, 1H, J2,3
10.4 Hz, J3,4 3.2 Hz, H-30), 5.10 (d, 1H, J1,2 8.0 Hz, H-
10), 4.88 (d, 1H, J1,2 8.0 Hz, H-1), 4.71 (dd, 1H, J5,6
6.0 Hz, J6,6 10.8 Hz, H-60), 4.44 (dd, 1H, J5,6 6.0 Hz,
J6,6 10.8 Hz, H-60), 4.36 (m, 1H, H-50), 4.23 (dd, 1H,
J2,3 10.4 Hz, J3,4 3.2 Hz, H-3), 4.21–4.19 (m, 2H, H-6,
H-5), 4.11 (dd, 1H, J5,6 6.0 Hz, J6,6 10.8 Hz, H-6), 2.00
(s, 3H, CH3CO). Anal. Calcd for C58H48Cl3NO18: C,
60.40; H, 4.19. Found: C, 60.26; H, 4.27.
3.19. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-6-O-acetyl-2,4-di-O-benzoyl-b-
D-galactopyranoside (23) and 4-methoxyphenyl 2,3,4,6-
tetra-O-benzoyl-a-D-galactopyranosyl-(1!3)-6-O-acetyl-
2,4-di-O-benzoyl-b-D-galactopyranoside (25)
Compounds
1 (3.3 g, 4.47 mmol) and 22 (2.0 g,
3.73 mmol) in dry CH2Cl2 (60 mL) were coupled by
the same procedure as described in the preparation of
3 to give disaccharide 23 (2.74 g, 66%) and 25 (665 mg,
16%), respectively, as foamy solids. Compound 23:
[a]D +53.1 (c 2.0, CHCl3); 1H NMR (400 MHz, CDCl3):
d 8.18–7.07 (m, 30H, 6PhH), 6.86 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.73 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
5.94 (d, 1H, J3,4 3.2 Hz, H-40), 5.87 (d, 1H, J3,4 3.2 Hz,
H-4), 5.81 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20),
5.58 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.40 (dd,
1H, J2,3 10.4 Hz, J3,4 3.2 Hz, H-30), 5.02 (d, 1H, J1,2
8.0 Hz, H-10), 4.99 (d, 1H, J1,2 8.0 Hz, H-1), 4.74 (dd,
1H, J5,6 6.0 Hz, J6,6 10.8 Hz, H-60), 4.34–4.30 (m, 2H,
H-60, H-50), 4.27 (dd, 1H, J2,3 10.4 Hz, J3,4 3.2 Hz,
H-3), 4.25–4.20 (m, 2H, H-6, H-5), 4.07 (dd, 1H, J5,6
4.8 Hz, J6,6 10.8 Hz, H-6), 3.65 (s, 3H, OCH3), 2.01 (s,
3H, CH3CO). Anal. Calcd for C63H54O19: C, 67.85; H,
3.21. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-6-O-acetyl-2,4-di-O-benzoyl-b-
D-galactopyranosyl-(1!3)-2,6,4-tri-O-benzoyl-b-D-
galactopyranoside (27) and 4- methoxyphenyl 2,3,4,6-
tetra-O-benzoyl-b-D-galactopyranosyl-(1!3)-6-O-acetyl-
2,4-di-O-benzoyl-a-D-galactopyranosyl-(1!3)-2, 4, 6-tri-
O-benzoyl-b-D-galactopyranoside (29)
A solution of 24 (1.4 g, 1.2 mmol) and 4-methoxyphenyl
2,4,6-tri-O-benzoyl-b-D-galactopyranoside (26, 600 mg,
1.0 mmol) in dry CH2Cl2 (100 mL) was stirred.
TMSOTf (50 lL) was added dropwise at ꢀ20 ꢁC with
nitrogen protection. The reaction mixture was stirred
for 2 h, during which time the temperature was gradu-
ally raised to ambient, and then the mixture was neutral-
ized with Et3N. Concentration of the reaction mixture,
followed by purification on a silica gel column with

A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
1959
2:1 petroleum ether–EtOAc as the eluent, gave 27
(955 mg, 60%) and 29 (286 mg, 18%), respectively, as
syrups. Compound 27: [a]D +68.4 (c 1.0, CHCl3); H
3.2 Hz, J2,3 10.4 Hz, H-300), 4.96 (d, 1H, J1,2 8.0 Hz,
H-100), 4.85 (d, 1H, J1,2 8.0 Hz, H-10), 4.79 (d, 1H, J1,2
8.0 Hz, H-1), 4.67–4.59 (m, 2H, 2H-600), 4.41 (dd, 1H,
J5,6 6.0 Hz, J6,6 10.4 Hz, H-60), 4.25–4.19 (m, 3H),
4.15–4.10 (m, 2H), 3.78 (m, 1H, H-5), 3.63 (s, 3H,
CH3O), 3.56–3.54 (m, 2H, 2H-60); 13C NMR
(100 MHz, CDCl3): d 166.3, 165.9, 165.8, 165.6, 165.5,
165.4, 164.4, 164.3, 164.0 (9C, 9COPh), 101.4, 101.3,
100.6 (3C, C-1). Anal. Calcd for C88H74O26: C, 68.30;
H, 4.82. Found: C, 68.49; H, 4.73.
1
NMR (400 Hz, CDCl3): d 8.03–7.24 (m, 45H, 9PhH),
6.78 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 6.51 (d, 2H, J
9.1 Hz, CH3OC6H4O–), 5.88 (d, 1H, J3,4 3.2 Hz, H-400),
5.82 (d, 1H, J3,4 3.6 Hz, H-40), 5.80 (d, 1H, J3,4 3.2 Hz,
H-4), 5.74 (m, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-200),
5.46 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20), 5.35 (m,
1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.23 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-300), 4.98 (d, 1H, J1,2 8.0 Hz, H-
100), 4.83 (d, 1H, J1,2 8.0 Hz, H-10), 4.79 (d, 1H, J1,2
8.0 Hz, H-1), 4.70–4.64 (m, 2H, H-600, H-600), 4.42 (dd,
1H, J5,6 6.0 Hz, J6,6 10.4 Hz, H-60), 4.29 (m, 1H, H-
500), 4.25–4.07 (m, 6H, H-60, H-30, H-3, H-50, 2H-6),
3.90 (m, 1H, H-5), 3.64 (s, 3H, CH3O), 2.04 (s, 3H,
CH3CO); 13C NMR (100 MHz, CDCl3): d 170.5 (1C,
CH3CO), 166.1, 165.9, 165.8, 165.5, 164.5, 165.4,
165.4, 164.3, 163.8 (9C, 9COPh), 101.4, 101.2, 100.9
(3C, C-1). Anal. Calcd for C90H76O27: C, 68.00; H,
4.82. Found: C, 67.89; H, 4.68. Compound 29: [a]D
+71.2 (c 1.0, CHCl3); 1H NMR (400 Hz, CDCl3): d
8.18–7.12 (m, 45H, 9PhH), 6.98 (d, 2H, J 9.1 Hz, CH3O-
C6H4O–), 6.67 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 5.99
(m, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-200), 5.88 (d, 1H,
J3,4 3.2 Hz, H-400), 5.82 (d, 1H, J3,4 3.6 Hz, H-40), 5.65
(d, 1H, J3,4 3.2 Hz, H-4), 5.52 (dd, 1H, J1,2 3.2 Hz, J2,3
10.4 Hz, H-20), 5.42 (m, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-2), 5.36 (d, 1H, J1,2 3.2 Hz, H-10), 5.31 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-300), 5.12 (d, 1H, J1,2 8.0 Hz, H-
100), 4.80 (d, 1H, J1,2 8.0 Hz, H-1), 4.52–4.48 (m, 2H,
H-600, H-600), 4.37–4.23 (m, 5H), 4.20–4.10 (m, 4H),
4.00 (m, 1H, H-5), 3.71 (s, 3H, CH3O), 1.99 (s, 3H,
CH3CO); 13C NMR (100 MHz, CDCl3): d 170.1 (1C,
CH3CO), 165.9, 165.7, 165.6, 165.4, 165.2, 165.2,
165.2, 165.0, 164.4 (9C, 9COPh), 101.3, 101.2, 93.5
(3C, C-1). Anal. Calcd for C90H76O27: C, 68.00; H,
4.82. Found: C, 68.15; H, 4.94.
3.23. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-[2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl]-2,4-
di-O-benzoyl-b-D-galactopyranosyl-(1!3)-2,4,6-tri-O-
benzoyl-b-D-galactopyranoside (30)
Compounds 9 (335 mg, 0.16 mmol) and 28 (200 mg,
0.13 mmol) in dry CH2Cl2 (50 mL) were coupled by
the same procedure as described in the preparation of
3 to give heptasaccharide 30 (385 g, 84%) as a syrup:
1
[a]D +79.3 (c 1.0, CHCl3); H NMR (400 Hz, CDCl3):
d 8.09–7.23 (m, 110H, 22PhH), 6.83 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.60 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.01 (d, 1H, J3,4 3.2 Hz, H-4), 5.90 (d, 1H, J3,4 3.2 Hz,
H-4), 5.86–5.82 (m, 2H, 2H-4), 5.79 (d, 1H, J3,4
3.2 Hz, H-4), 5.71 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-2), 5.69 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2),
5.68–5.64 (m, 2H), 5.61 (d, 1H, J3,4 3.2 Hz, H-4), 5.59
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.57–5.50 (m,
3H), 5.48 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.40
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.35 (dd, 1H,
J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.26 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.20 (dd, 1H, J3,4 3.2 Hz,
J2,3 10.4 Hz, H-3), 4.75 (d, 1H, J1,2 8.0 Hz, H-1), 4.73
(d, 1H, J1,2 8.0 Hz, H-1), 4.69 (dd, 1H, J5,6 5.4 Hz, J6,6
11.2 Hz, H-6), 4.65 (d, 1H, J1,2 8.0 Hz, H-1), 4.61 (d,
1H, J1,2 8.0 Hz, H-1), 4.58 (d, 1H, J1,2 8.0 Hz, H-1),
4.33 (d, 1H, J1,2 8.0 Hz, H-1), 4.30 (d, 1H, J1,2 8.0 Hz,
H-1), 3.66 (s, 3H, CH3O); 13C NMR (100 MHz, CDCl3):
d 167.1, 166.0, 165.9, 165.9, 165.9, 165.8, 165.7, 165.7,
165.6, 165.6, 165.5, 165.4, 165.4, 165.3, 165.2, 165.2,
165.1, 165.1, 165.0, 164.4, 164.3, 163.8 (22C, 22COPh),
101.2, 101.1, 101.1, 101.0, 100.7, 100.6, 100.1 (7C, C-
1). Anal. Calcd for C203H166O59: C, 68.69; H, 4.71.
Found: C, 68.47; H, 4.83.
3.22. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-2,4-di-O-benzoyl-b-D-galacto-
pyranosyl-(1!3)-2,4,6-tri-O-benzoyl-b-D-galacto-
pyranoside (28)
To a solution of 27 (956 g, 0.60 mmol) in 1:1 CH3OH–
CH2Cl2 (40 mL) was added CH3COCl (0.4 mL), and
the reaction was carried out by the same procedure as
described in the preparation of 7 to give 28 (781 mg,
1
84%) as a syrup: [a]D +28.7 (c 1.0, CHCl3); H NMR
(400 Hz, CDCl3): d 8.03–7.11 (m, 45H, 9PhH), 6.76 (d,
2H, J 9.1 Hz, CH3OC6H4O–), 6.50 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 5.89 (d, 1H, J3,4 3.6 Hz, H-400), 5.81
(m, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-200), 5.77 (d, 1H,
J3,4 3.6 Hz, H-40), 5.68 (d, 1H, J3,4 3.2 Hz, H-4), 5.45
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-20), 5.40 (m, 1H,
J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.24 (dd, 1H, J3,4
3.24. 4-Methoxyphenyl b-D-galactopyranosyl-(1!3)-[b-
D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-(1!6)-
b-D-galactopyranosyl-(1!6)-b-D-galactopyranosyl]-b-D-
galactopyranosyl-(1!3)-b-D-galactopyranoside (31)
Compound 30 (385 mg, 0.11 mmol) was dissolved in a
satd solution of NH3 in MeOH (50 mL). After a week

1960
A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
at rt, the reaction mixture was concentrated, and the res-
idue was purified by chromatography on Sephadex LH-
20 (MeOH) to afford 31 as an amorphous solid (175 mg,
81%): [a]D +56.7 (c 1.0, H2O); 1H NMR (D2O,
400 MHz): d 7.06 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.91 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 4.94 (m, 2H,
2H-1), 4.74 (d, H, J1,2 8.0 Hz, 2H-1), 4.64 (d, 1H, J1,2
7.6 Hz, H-1), 4.55 (d, 1H, J1,2 8.0 Hz, H-1), 4.39
(d, 1H, J1,2 7.2 Hz, H-1), 4.37 (d, 1H, J1,2 7.2 Hz,
H-1); 13C NMR (100 MHz, D2O):d 104.4, 104.3,
103.8, 103.4, 103.4, 100.3, 101.4 (7C, C-1). MALDI-
TOFMS Calcd for C49H78O37: 1259.11 [M]. Found:
1259.6 [M].
3.26. 4-Methoxyphenyl b-D-galactopyranosyl-(1!3)-[b-
D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-(1!6)-
b-D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-
(1!6)-b-D-galactopyranosyl]-b-D-galactopyranosyl-
(1!3)-b-D-galactopyranoside (33)
Compound 32 (385 mg, 0.096 mmol) was dissolved in a
satd solution of NH3 in MeOH (50 mL). After a week at
rt, the reaction mixture was concentrated, and the resi-
due was purified by chromatography on Sephadex
LH-20 (MeOH) to afford 33 as an amorphous solid
(135 mg, 84%): [a]D +71.3 (c 1.0, H2O); 1H NMR
(D2O, 400 MHz): d 6.97 (d, 2H, J 9.1 Hz, CH3O-
C6H4O–), 6.84 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 4.90
(m, 2H, 2H-1), 4.77 (d, 1H, J1,2 8.0 Hz, H-1), 4.68 (d,
1H, J1,2 7.8 Hz, H-1), 4.59 (d, 1H, J1,2 7.6 Hz, H-1),
4.48 (d, 1H, J1,2 8.0 Hz, H-1), 4.35 (m, 2H, 2H-1); 13C
NMR (100 MHz, D2O):d 104.0, 103.8, 103.6, 103.2,
103.1, 103.1, 101.2, 101.1 (8C, 8C-1). MALDI-TOFMS
Calcd for C55H88O42: 1421.25 [M]. Found: 1421.4 [M].
3.25. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-[2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl]-2,4-
di-O-benzoyl-b-D-galactopyranosyl-(1!3)-2,4,6-tri-O-
benzoyl-b-D-galactopyranoside (32)
3.27. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-[2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-
2,3,4-tri-O-benzoyl-b-D-galactopyranosyl]-2,4-di-O-benz-
oyl-b-D-galactopyranosyl-(1!3)-2,4,6-tri-O-benzoyl-b-D-
galactopyranoside (34)
Compounds 15 (409 mg, 0.16 mmol) and 28 (200 mg,
0.13 mmol) in dry CH2Cl2 (50 mL) were coupled by
the same procedure as described in the preparation of
3 to give octasaccharide 32 (410 g, 79%) as a syrup:
1
[a]D +83.4 (c 1.0, CHCl3); H NMR (400 Hz, CDCl3):
d 8.02–7.21 (m, 125H, 25PhH), 6.84 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.60 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
5.99 (d, 1H, J3,4 3.2 Hz, H-4), 5.91 (d, 1H, J3,4 3.4 Hz,
H-4), 5.89 (d, 1H, J3,4 3.4 Hz, H-4), 5.86 (d, 1H, J3,4
3.2 Hz, H-4), 5.82 (d, 1H, J3,4 3.2 Hz, H-4), 5.77 (d,
1H, J3,4 3.2 Hz, H-4), 5.68 (dd, 1H, J1,2 8.0 Hz, J2,3
10.4 Hz, H-2), 5.67 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-2), 5.65–5.63 (m, 2H), 5.61 (d, 1H, J3,4 3.2 Hz, H-4),
5.59 (d, 1H, J3,4 3.2 Hz, H-4), 5.57–5.51 (m, 3H), 5.49
(dd, 1H, J3,4 3.4 Hz, J2,3 10.4 Hz, H-3), 5.46 (dd, 1H,
J3,4 3.4 Hz, J2,3 10.4 Hz, H-3), 5.43 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.40 (dd, 1H, J3,4 3.2 Hz,
J2,3 10.4 Hz, H-3), 5.37 (dd, 1H, J3,4 3.4 Hz, J2,3
10.4 Hz, H-3), 5.27 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz,
H-2), 5.21 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 4.77
(d, 1H, J1,2 8.0 Hz, H-1), 4.72 (d, 1H, J1,2 8.0 Hz, H-
1), 4.70 (d, 1H, J1,2 8.0 Hz, H-1), 4.65 (dd, 1H, J5,6
5.4 Hz, J6,6 11.2 Hz, H-6), 4.55 (d, 1H, J1,2 8.0 Hz, H-
1), 4.52 (d, 1H, J1,2 8.0 Hz, H-1), 4.46 (d, 1H, J1,2
8.0 Hz, H-1), 4.32 (d, 1H, J1,2 8.0 Hz, H-1), 4.29 (d,
1H, J1,2 8.0 Hz, H-1), 3.68 (s, 3H, CH3O); 13C NMR
(100 MHz, CDCl3): d 165.9, 165.9, 165.9, 165.8, 165.8,
165.6, 165.6, 165.5, 165.5, 165.5, 165.4, 165.4, 165.4,
165.3, 165.3, 165.2, 165.1, 165.1, 165,0, 165.0, 164.9,
164.9, 164.8, 164.4, 164.4 (25C, 25COPh), 101.4, 101.0,
101.0, 101.9, 101.9, 100.7, 100.5, 100.0 (8C, C-1). Anal.
Calcd for C230H188O67: C, 68.65; H, 4.71. Found: C,
68.91; H, 4.68.
Compounds 17 (434 mg, 0.14 mmol) and 28 (200 mg,
0.116 mmol) in dry CH2Cl2 (20 mL) were coupled by
the same procedure as described in the preparation of
3 to give nonasaccharide 34 (453 mg, 78%) as a syrup:
1
[a]D +81.7 (c 1.0, CHCl3); H NMR (400 Hz, CDCl3):
d 8.01–7.21 (m, 140H, 28PhH), 6.84 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.61 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.05 (d, 1H, J3,4 3.2 Hz, H-4), 5.91 (d, 1H, J3,4 3.2 Hz,
H-4), 5.85–5.83 (m, 3H), 5.82 (d, 1H, J3,4 3.2 Hz, H-4),
5.78 (d, 1H, J3,4 3.2 Hz, H-4), 5.73 (d, 1H, J3,4 3.2 Hz,
H-4), 5.71 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.69
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.67–5.61 (m,
3H), 5.59 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.54
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.52–5.49 (m,
4H), 5.46 (dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.44
(dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.42 (dd, 1H,
J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.37 (dd, 1H, J1,2
8.0 Hz, J2,3 10.4 Hz, H-2), 5.27 (dd, 1H, J1,2 8.0 Hz,
J2,3 10.4 Hz, H-2), 5.21 (dd, 1H, J3,4 3.2 Hz, J2,3
10.4 Hz, H-3), 4.77 (d, 1H, J1,2 8.0 Hz, H-1), 4.72 (d,
1H, J1,2 8.0 Hz, H-1), 4.62 (d, 1H, J1,2 8.0 Hz, H-1),
4.55 (d, 1H, J1,2 8.0 Hz, H-1), 4.46 (d, 1H, J1,2 8.0 Hz,
H-1), 4.36–4.34 (m, 2H, H-1), 4.30 (d, 1H, J1,2 8.0 Hz,
H-1), 4.27 (d, 1H, J1,2 8.0 Hz, H-1), 3.67 (s, 3H,
CH3O); 13C NMR (100 MHz, CDCl3): d 167.1, 166.9,

A. Li, F. Kong / Carbohydrate Research 340 (2005) 1949–1962
1961
166.7, 166.6, 166.5, 166.5, 166.1, 166.0, 165.0, 165.9,
165.9, 165.8, 165.7, 165.7, 165.6, 165.6, 165.5, 165.4,
165.4, 165.3, 165.3, 165.2, 165.1, 165.1, 165.0, 164.4,
164.3, 164.0 (28C, 28COPh), 101.3, 101.2, 101.2, 101.1,
101.0, 100.9, 100.6, 100.4, 100.3 (9C, C-1). Anal. Calcd
for C257H210O75: C, 68.62; H, 4.70. Found: C, 68.55;
H, 4.81.
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.48–5.46 (m,
4H), 5.43 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.41
(dd, 1H, J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.39 (dd, 1H,
J3,4 3.2 Hz, J2,3 10.4 Hz, H-3), 5.38–5.35 (m, 2H), 5.34
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.28 (dd, 1H,
J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.20 (dd, 1H, J3,4
3.2 Hz, J2,3 10.4 Hz, H-3), 4.78 (d, 1H, J1,2 8.0 Hz, H-
1), 4.73 (d, 1H, J1,2 8.0 Hz, H-1), 4.63–4.61 (m, 2H, H-
1), 4.43 (d, 1H, J1,2 8.0 Hz, H-1), 4.41 (d, 1H, J1,2
8.0 Hz, H-1), 4.35 (d, 1H, J1,2 8.0 Hz, H-1), 4.33–4.30
(m, 2H, 2H-1), 4.27 (d, 1H, J1,2 8.0 Hz, H-1), 3.67 (s,
3H, CH3O); 13C NMR (100 MHz, CDCl3): d 167.5,
167.3, 167.2, 167.0, 167.0, 167.9, 166.8, 166.8, 166.7,
166.6, 166.3, 166.0, 166.0, 165.9, 165.8, 165.8, 165.7,
165.6, 165.6, 165.5, 165.5, 165.4, 165.3, 165.3, 165.2,
165.2, 165.1, 165.0, 164.9, 164.7, 164.3 (31C, 31COPh),
101.4, 101.3, 101.1, 101.1, 101.0, 100.9, 100.7, 100.7,
100.3, 100.1 (10C, C-1). Anal. Calcd for C284H232O83:
C, 68.59; H, 4.70. Found: C, 68.42; H, 4.93.
3.28. 4-Methoxyphenyl b-D-galactopyranosyl-(1!3)-[b-
D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-(1!6)-
b-D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-
(1!6)-b-D-galactopyranosyl-(1!6)-b-D-galactopyrano-
syl]-b-D-galactopyranosyl-(1!3)-b-D-galactopyranoside
(35)
Compound 34 (400 mg, 0.089 mmol) was dissolved in a
satd solution of NH3 in MeOH (80 mL). After a week at
rt, the reaction mixture was concentrated, and the resi-
due was purified by chromatography on Sephadex
LH-20 (MeOH) to afford 35 as an amorphous solid
(114 mg, 81%): [a]D +62.1 (c 1.0, H2O); 1H NMR
(D2O, 400 MHz): d 7.00 (d, 2H, J 9.1 Hz, CH3O-
C6H4O–), 6.91 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 4.92
(m, 2H, 2H-1), 4.80 (d, 1H, J1,2 8.0 Hz, H-1), 4.64 (d,
1H, J1,2 7.6 Hz, H-1), 4.57 (d, 1H, J1,2 8.0 Hz, H-1),
4.46 (d, 2H, J1,2 7.2 Hz, 2H-1), 4.38 (d, H, J1,2 8.0 Hz,
H-1), 4.35 (d, H, J1,2 8.0 Hz, H-1); 13C NMR
(100 MHz, D2O):d 104.2, 104.0, 103.7, 103.2, 103.2,
103.2, 101.2, 102.2, 101.1 (9C, 9C-1). MALDI-TOF
MS Calcd for C61H98O47: 1583.39 [M]. Found: 1583.2
[M].
3.30. 4-Methoxyphenyl b-D-galactopyranosyl-(1!3)-[b-
D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-(1!6)-
b-D-galactopyranosyl-(1!6)-b-D-galactopyranosyl-
(1!6)-b-D-galactopyranosyl-(1!6)-b-D-galactopyranos-
yl-(1!6)-b-D-galactopyranosyl]-b-D-galactopyranosyl-
(1!3)-b-D-galactopyranoside (37)
Compound 36 (234 mg, 0.047 mmol) was dissolved in a
satd solution of NH3 in MeOH (50 mL). After a week at
rt, the reaction mixture was concentrated, and the resi-
due was purified by chromatography on Sephadex
LH-20 (MeOH) to afford 37 as an amorphous solid
1
3.29. 4-Methoxyphenyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!3)-[2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galacto-
pyranosyl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranos-
yl-(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-
(1!6)-2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-
2,3,4-tri-O-benzoyl-b-D-galactopyranosyl-(1!6)-2,3,4-
tri-O-benzoyl-b-D-galactopyranosyl]-2,4-di-O-benzoyl-b-
D-galactopyranosyl-(1!3)-2,4,6-tri-O-benzoyl-b-D-
galactopyranoside (36)
(74 mg, 90%): [a]D +43.7 (c 1.0, H2O); H NMR (D2O,
400 MHz): d 7.98 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.82 (d, 2H, J 9.1 Hz, CH3OC6H4O–), 4.90 (m, 2H,
2H-1), 4.85 (d, 1H, J1,2 8.0 Hz, H-1), 4.68 (d, 1H, J1,2
8.0 Hz, H-1), 4.59 (d, 1H, J1,2 7.6 Hz, H-1), 4.48 (d,
2H, J1,2 7.2 Hz, 2H-1), 4.41 (d, 1H, J1,2 7.6 Hz, H-1),
4.36 (m, 2H, 2H-1); 13C NMR (100 MHz, D2O):d
104.6, 104.5, 104.2, 103.8, 103.3, 100.3, 103.2, 103.1,
101.3, 101.2 (10C, 10C-1). MALDI-TOF MS Calcd
for C67H108O52: 1745.53 [M]. Found: 1745.3 [M].
Compounds 19 (278 mg, 0.077 mmol) and 28 (100 mg,
0.065 mmol) in dry CH2Cl2 (50 mL) were coupled by
the same procedure as described in the preparation of
3 to give decasaccharide 36 (234 mg, 73%) as a syrup:
Acknowledgements
This work was supported by The National Natural Sci-
ence Foundation of China (Projects 30070185 and
39970864).
1
[a]D +52.3 (c 1.0, CHCl3); H NMR (400 Hz, CDCl3):
d 7.79–7.23 (m, 155H, 31PhH), 6.84 (d, 2H, J 9.1 Hz,
CH3OC6H4O–), 6.61 (d, 2H, J 9.1 Hz, CH3OC6H4O–),
6.04 (d, 1H, J3,4 3.2 Hz, H-4), 5.93 (d, 1H, J3,4 3.2 Hz,
H-4), 5.87 (d, 1H, J3,4 3.2 Hz, H-4), 5.85–5.83 (m, 4H),
5.80 (d, 1H, J3,4 3.2 Hz, H-4), 5.77 (d, 1H, J3,4 3.2 Hz,
H-4), 5.63 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.61
(dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.60–5.58 (m,
3H), 5.53 (dd, 1H, J1,2 8.0 Hz, J2,3 10.4 Hz, H-2), 5.50
References
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