Alternative synthesis of radioiodinated trisaccharide derivatives, 2-(4-125iodophenyl)ethyl 2-acetamido-2-deoxy-β-d-glucopyranosyl- (1→2)-α-d-mannopyranosyl-( 1→6)-β-d-glucopyranoside, and preparation of its analogs having different lengths of

Article abstract of DOI:10.3987/COM-11-12332

A radioiodinated artificial substrate of N-acetylglucosaminyltransferase V (GnT-V), 2-(4-iodophenyl)ethyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1 → 2)-α-D-mannopyranosyl-(1 → 6)-β-D-glucopyranoside ([ ¹²⁵I]1a), was alternatively synthesized b

Full text of DOI:10.3987/COM-11-12332

HETEROCYCLES, Vol. 83, No. 12, 2011
2779
HETEROCYCLES, Vol. 83, No. 12, 2011, pp. 2779 - 2802. © 2011 The Japan Institute of Heterocyclic Chemistry
Received, 9th August, 2011, Accepted, 30th September, 2011, Published online, 13th October, 2011
DOI: 10.3987/COM-11-12332
ALTERNATIVE
SYNTHESIS
OF
RADIOIODINATED
TRISACCHARIDE
DERIVATIVES,
2-(4-125IODOPHENYL)ETHYL
2-ACETAMIDO-2-DEOXY--D-GLUCOPYRANOSYL-(1→2)--D-MANNO-
PYRANOSYL-(1→6)--D-GLUCOPYRANOSIDE, AND PREPARATION
OF ITS ANALOGS HAVING DIFFERENT LENGTHS OF ALKYL
CHAINS INSTEAD OF ETHYL GROUP: ACCEPTOR SUBSTRATES OF
N-ACETYLGLUCOSAMINYLTRANSFERASE
V
FOR IN VIVO
IMAGING
Kenji Arimitsu,a Tetsuya Kajimoto,a,c Hiroyuki Kimura,b Masahiro Ono,b
Minoru Ozeki,a Manabu Node,a Yoshiro Ohmomo,c Hideo Saji,b* and
Masayuki Yamashitaa*
a
Kyoto Pharmaceutical University, Shichono-cho, Yamashina-ku, Kyoto
b
607-8414, Japan,
Graduate School of Pharmaceutical Sciences, Kyoto
University, Yoshida Shimoadachi-cho, Sakyo-ku, Kyoto 606-8501, Japan, c Osaka
University of Pharmaceutical Sciences, 4-1-20 Nasahara, Takatsuki, Osaka
569-1094, Japan.
yamasita@mb.kyoto-phu.ac.jp
Abstract – A radioiodinated artificial substrate of N-acetylglucosaminyl-
transferase V (GnT-V), 2-(4-iodophenyl)ethyl 2-acetamido-2-deoxy--D-gluco-
pyranosyl-(1 → 2)--D-mannopyranosyl-(1 → 6)--D-glucopyranoside ([125I]1a),
was alternatively synthesized by using the glycosylation reaction from the
non-reducing end, in which a glycosyl sulfoxide and a thioglycoside were
employed as the glycosyl acceptor and donor, respectively. In addition, two
derivatives of [125I]1a having different lengths of alkyl chain ([125I]1b, [125I]1c)
were prepared in the same way to increase the permeability of the substrates
through the cell membrane and into the Golgi apparatus, where GnT-V acts to
modify glycoconjugates by transferring N-acetylglucosamine units from
UDP-GlcNAc.

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HETEROCYCLES, Vol. 83, No. 12, 2011
INTRODUCTION
Glycoconjugates on the cell surfaces play important roles in many biological events, which relate to cell
adhesions. The recent development of glycosciences and cancer research revealed a close relationship
between the expression of glycoconjugates carrying highly antennary sugar chains on cell surfaces and
malignant transformation of tumor cells. A number of studies in the last two decades showed that
N-acetylglucosaminyltransferase V (GnT-V) is one of the most relevant glycosyltransferases for tumor
invasion and metastasis.1-10
Recently, we reported the synthesis of the radioiodinated trisaccharide derivative, 2-(p-iodophenyl)ethyl
2-acetamido-2-deoxy--D-glucopyranosyl-(1 → 2)--D-mannopyranosyl-(1 → 6)--D-glucopyranoside
([125I]IPGMG, [125I]1a), and its high specificity to GnT-V, which was confirmed by efficient
transformation from [125I]1a to (1→6)GlcNAc-bearing [125I]IPGMG ([125I]IPGGMG, [125I]2) in vitro
assay (Figure 1).11 Being proceeded via a labile intermediate of glycosyl bromide 6, the synthetic route
requires preparation each time of 6 to apply for the synthesis of analogs and derivatives of [125I]1a even
when the structural differences were quite small.
Meanwhile, increased permeability of molecules through the cell membrane and into Golgi apparatus,
which depends on their hydrophobicity, is very important when designing substrates and inhibitors of
glycosyltransferarses since most glycosyltransferases act in the Golgi apparatus. Thus, the derivatives
([125I]1b-c) of [125I]1a bearing longer alkyl chains than p-iodophenylethyl group, i.e., p-iodophenyloctyl
or p-iodophenylpentadecyl groups, are expected to behave as more reliable and useful substrates to
investigate the activity of GnT-V than [125I]1a, not only in vitro but also in vivo.
In advance of the above study, we synthesized 2-(trimethylsilyl)ethyl 2-acetamido-3,4,6-tri-O-acetyl-
2-deoxy--D-glucopyranosyl-(1 → 2)-3-O-benzyl-4,6-O-benzylidene--D-mannopyranosyl-(1 → 6)-2,3,4-
tri-O-benzyl--D-glucopyranoside (9) carrying the same sugar chain as [125I]1a-c using odorless
benzenethiols, such as p-octyloxybenzenethiol and p-dodecylbenzenethiol, as the activating group of
glycosyl donors in the glycosylation reaction.12,13 On the other hand, we reported a novel glycosylation
method from the non-reducing end using glycosyl sulfoxides as glycosyl acceptors, which was prepared
by oxidation of the p-octyloxyphenyl thioglycosides.14 In this strategy, the resulting glycosyl sulfoxide
was reduced to the corresponding thioglycoside, which was employed as the glycosyl donor in the
following glycosylation reaction. This strategy was effective, especially when N-acetylglucosamine
residue was presented at the non-reducing end, such as [125I]1a-c. 14
In the present paper, we report an alternative synthetic route of [125I]1a, which was applicable to the
synthesis of [125I]1b-c and proceeded via a stable synthetic intermediate.

HETEROCYCLES, Vol. 83, No. 12, 2011
2781
HO
HO
HO
HO
HO
HO
O
O
O
O
OH
OH
AcHN
O
AcHN
AcHN
OH
OH
OH
O
OH
O
OH
OH
O
O
O
O
O
O
O
HO
HO
HO
HO
OH
125I]IPGMG ([125I]1a)
OH
125I]IPGGMG ([125I]2a)
125I
125I
[
[
Figure 1. The transfer of a GlcNAc residue from UDP-GlcNAc to [125I]1 to form [125I]2 by GnT-V
RESULTS AND DISCUSSION
On the basis of our previous works,11-14 two synthetic routes were attempted to obtain [125I]1a-c, as shown
in Scheme 1. One was designed by retro-synthesis that cleaved the glycosyl bond between the aglycon
and the reducing end of the sugar moiety. According to this strategy, [125I]1a-c seemed to be capable of
being synthesized by the glycosylation of p-iodophenyl alcohols 5a-c with the trisaccharyl donor 4
(Scheme1, route A). Herein, trichloroacetimidate 4 could be derived by cleavage of the trimethylsilylethyl
group from trisaccharide 3, for which the synthetic precursor 9 was previously synthesized as part of our
glycosylation study using thioglycosides prepared from odorless benezenethiols,12,13 followed by
trichloroacetimidation using the Schmidt method; however, subsequent glycosylation of 5b with 4 in the
presence of TMSOTf did not afford the desired product 10b but orthoester 11 (15%), recovering the intact
imidate 4 (79%) (Scheme 2). The other route was retro-synthesized by the glycosylation of
monoglucosides 8a-c with disaccharyl donor 7 (Scheme 1, route B). In contrast to our recent study on the
synthesis of 1a,11 where the labile intermediate of disaccharyl bromide 6 was chosen as the glycosyl
donor for glycosylation, we herein adopted disaccharyl sulfide 7, which could be provided by reduction of
the sulfoxide group and replacement of the protecting groups in 12.14
AcO
AcO
AcO
O
O
OAc
AcO
AcO
AcO
HO
HO
HO
O
O
AcHN
O
O
O
OAc
OAc
OAc
OH
AcHN
AcHN
O
O
O
OAc
OAc
OH
OH
Route B
Route A
O
AcO
AcO
R1
O
X
6 : X = Br
7 : X = SPh-4-OC8H17
2
AcO
O
n
R
O
HO
HO
+
3 : R1 = OCH2CH2TMS, R2 = H
4 : R1 = H, R2 = OC(=NH)CCl3
OH
125I
HO
AcO
AcO
n
O
O
+
[
[
[
125I]1a : n = 1 ([125I]IPGMG)
125I]1b : n = 7
125I]1c : n = 14
AcO
8a-c
n
HO
I
I
5a-c
Scheme 1. Retrosynthetic strategy of [125I] radiolabeled trisaccharide derivatives ([125I]1a-c)

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HETEROCYCLES, Vol. 83, No. 12, 2011
AcO
AcO
AcO
O
O
AcO
AcO
AcO
AcO
O
O
O
O
OAc
AcO
AcHN
OAc
AcO
OAc
AcHN
O
AcHN
OAc
OAc
O
O
O
OAc
OAc
a, b
c, d
Ph
O
O
3
4
O
O
87%
(2 steps)
69%
(2 steps)
O
AcO
AcO
O
7
O
O
O
BnO
BnO
AcO
AcO
I
TMS
O
O
7
BnO
AcO
10b
I
O
9
11
15%
a: H2, Pd(OH)2/C, MeOH, b: Ac2O, DMAP, pyridine, c: TFA, CH2Cl2, d: CCl3CN, DBU, CH2Cl2.
Scheme 2. Attempted synthesis of trisaccharide 10b
Thus, the disaccharyl sulfoxide 12, which was prepared by our glycosylation method using glycosyl
sulfoxide and thioglycoside as the acceptor and the donor, respectively,14 was reduced with
triphenylphosphine and carbon tetrachloride in MeCN to afford the thio-disaccharide 13 in good yield
(92%). The phthaloyl group of 13 was removed with hydrazine hydrate, followed by acetylation to give
the acetamide 14. Since catalytic hydrogenation was not applicable for deprotection of the benzylidene
and benzyl groups of 14 due to the presence of a sulfide group,15 the benzylidene group of 14 was first
cleaved by acetic acid in THF to afford diol 15, the benzyl group of which was subsequently deprotected
by treatment with trimethylsilyl chloride and lithium iodide16 in CHCl3 to afford triol 16 (96%). The
disaccharide 16 was peracetylated to 7 by a conventional acetylation reaction with acetic anhydride and
pyridine.
AcO
AcO
AcO
AcO
AcO
AcO
O
AcO
AcO
AcO
O
O
O
O
O
OBn
OBn
OBn
a
b, c
AcHN
PhthN
PhthN
O
O
O
O
O
O
Ph
Ph
Ph
O
92%
86%
(2 steps)
O
O
C8H17
O
S
C8H17
O
S
C8H17
O
S
O
14
12
13
AcO
AcO
AcO
AcO
AcO
AcO
AcO
AcO
AcO
O
O
O
O
O
O
OAc
d
e
c
OBn
OH
AcHN
AcHN
AcHN
O
OAc
OAc
O
O
OH
OH
OH
OH
86%
96%
90%
C8H17
O
S
C8H17
O
S
C8H17
O
S
7
16
15
a: PPh3, CCl4, MeCN, b: NH2NH2 .H2O, EtOH-toluene, c: Ac2O, DMAP, pyridine, d: 70 % AcOH aq., THF, e: TMSCl, LiI, CHCl3.
Scheme 3. Synthesis of disaccharide 7

HETEROCYCLES, Vol. 83, No. 12, 2011
2783
Meanwhile, 4-iodophenylalkyl 2,3,4-tri-O-acetyl--D-glucopyranosides (8a-c) were synthesized by
glucosylation and deprotection of the allyloxycarbonyl (Alloc) group at C-6 (Scheme 4). While 5a was
commercially available, alcohol 5b was prepared by iodination of 8-phenyl-1-octanol using triflic acid
and NIS, and 5c was synthesized by a well-established method reported by Weichert and his colleagues.17
.
Glucosylation of 5a-c with the imidate 1711 in the presence of BF3 Et2O in CH2Cl2 at 20 ˚C afforded
18a-c in 62%, 63%, and 71%, respectively. The Alloc group at the C-6 position of the glucose residue in
18a-c was removed with tetrakis(triphenylphosphine)palladium(0) in the presence of formic acid to afford
8a-c,11,18 which would be an acceptor substrate in the following glycosylation.
AllocO
O
AcO
AcO
AcO
O
CCl3
NH
AllocO
n
O
HO
AcO
AcO
a
b
n
O
17
O
AcO
O
AcO
+
AcO
AcO
I
n
I
HO
18a : n = 1 (62%)
18b : n = 7 (63%)
18c : n = 14 (71%)
8a : n = 1 (95%)
8b : n = 7 (94%)
8c : n = 14 (96%)
I
5a-c
a: BF3 .Et2O, CH2Cl2, b: Pd(PPh3)4, PPh3, HCO2H, THF.
Scheme 4. Syntheses of 4-iodophenylalkyl glycosides 8a-c
Next, glycosylation of 8a-c with thio-disaccharide 7 was performed in the presence of triflic acid and NIS
to yield 10a-c.19 It is noteworthy that the chemical yield was elevated from 67% to 86% by changing the
bromide 6 to 7 as the glycosyl donor.11 Subsequent deacetylation of 10a-c with sodium methoxide in
methanol afforded the non-labeled products 1a-c (Scheme 5).
HO
HO
HO
O
AcO
AcO
AcO
O
O
O
OH
OAc
AcHN
AcHN
O
OH
OH
a
b
O
OAc
OAc
7 + 8a-c
O
O
n
O
n
O
O
HO
HO
O
AcO
AcO
OH
AcO
I
I
1a : n = 1 (79%)
1b : n = 7 (77%)
1c : n = 14 (73%)
10a : n = 1 (86%)
10b : n = 7 (82%)
10c : n = 14 (85%)
a: NIS, TfOH, MS4A, CH2Cl2, b: NaOMe, MeOH.
Scheme 5. Syntheses of trisaccharides 1a-c

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HETEROCYCLES, Vol. 83, No. 12, 2011
Finally, in order to synthesize the desired radioiodinated compounds [125I]1a-c, non-labeled iodo group of
10a-c was exchanged for a tributyltin group using a combination of Pd(PPh3)4, PPh3, and (Bu3Sn)2 or that
of PdCl2(dppf), KOAc, and (Bu3Sn)2,20 to afford 19a-c in good yield (61%, 31%, and 16%, respectively).
Replacement of the stannyl group with the radioactive iodo group was performed by iodo-destannylation
reaction.11, 21 Namely, the stannylphenyl moiety of 19a-c was reacted with 125I2, which was prepared by a
oxidation reaction of commercially available [125I]NaI with H2O2, to afford the radioiodinated
trisaccharide derivatives 10a-c via iodostannyl aronium intermediates 20a-c. The following deacetylation
of [125I]10a-c with sodium methoxide in methanol gave [125I]1a-c. The radiochemical identity of
[125I]1a-c was verified by co-injection with nonradioactive 1a-c by their HPLC profiles. Radioactive
[125I]1a-c showed a single radioactive peak at the same retention time as that of nonradioactive 1a-c.
Radiochemical yields of [125I]1a-c were 71%, 76% and 54%, respectively. The radiochemical purities
after purification by HPLC were >99%, >99% and >99%, respectively (Scheme 6).
AcO
AcO
AcO
AcO
AcO
AcO
O
O
O
O
OAc
OAc
AcHN
AcHN
O
OAc
OAc
O
OAc
OAc
c
a or b
O
O
10a-c
n
O
n
O
O
O
AcO
AcO
AcO
AcO
AcO
AcO
SnBu3
SnBu3
125I
20a-c
19a : n = 1 (61%)
19b : n = 7 (31%)
19c : n = 14 (16%)
HO
HO
HO
O
AcO
AcO
AcO
O
O
O
OH
OAc
AcHN
AcHN
O
OH
O
OAc
OAc
OH
d
O
O
n
O
n
O
O
HO
HO
O
AcO
AcO
OH
AcO
125I]10a-c
125I
125I
125I]1a : n = 1 (71%)
125I]1b : n = 7 (76%)
125I]1c : n = 14 (54%)
[
[
[
[
a: Pd(PPh3)4, PPh3, (n-Bu3Sn)2, toluene, b : PdCl2(dppf), KOAc, (n-Bu3Sn)2, NMP, c: [125I]NaI, 5 % H2O2 aq., 0.1 M HCl aq. MeCN, d: NaOMe, MeOH.
Scheme 6. Radiosyntheses of trisaccharides [125I]1a-c
We successfully synthesized a series of trisaccharide derivatives 1a-c having different lengths of alkyl
chain with 2, 8 and, 15 carbons on the basis of our previous glycosylation method, with glycosyl
sulfoxides and thioglycosides as the acceptor and the donor, respectively. Moreover, by using iodo→tin
and tin→iodo exchange reactions, we succeeded in synthesizing radioiodinated [125I]1a-c.

HETEROCYCLES, Vol. 83, No. 12, 2011
2785
EXPERIMENTAL
General. Infrared (IR) spectra were recorded on a Shimadzu FTIR-8300 diffraction grating infrared
1
spectrophotometer and H-NMR spectra were obtained on a JEOL JNM-AL400 spectrometer with
tetramethylsilane as an internal standard in the case of CDCl3. 13C-NMR spectra were obtained on a JEOL
JNM-AL400 spectrometer with C5D5N as the internal standard. Mass spectra (MS) were determined on a
JEOL JMS-SX 102A QQ or a JEOL JMS-GC-mate mass spectrometer. Specific rotations were recorded
on a Horiba SEPA-200 automatic digital polarimeter. Wakogel C-200 (silica gel) (100-200 mesh; Wako)
was used for open column chromatography. Flash column chromatography was performed by using Silica
Gel 60N (Kanto Chemical Co., Inc.) as a solid support in the immobile phase. Kieselgel 60 F-254 plates
(Merck) were used for thin layer chromatography (TLC). Preparative TLC (PTLC) was conducted with a
Kieselgel 60 F-254 plate (0.25 mm; Merck) or Silica gel 60 F-254 plate (0.5 mm; Merk). Unless
purification with silica gel gave a pure enough compound, the compounds were further treated with
recycling HPLC (JAI LC-908) on a GPC column (JAIGEL 1H and 2H).
Materials. Most reagents were obtained from Wako Pure Chemical Industries, Ltd., Nacalai Tesque, Inc.,
and Aldrich Chemical Inc. 5a and 5c are known compounds.
8-(p-Iodophenyl) octanol (5b)
N-Iodosuccinimide (1.08 g, 4.80 mmol) and triflic acid (386 L, 4.36 mmol) were added to a solution of
8-phenyloctanol (900.1 mg, 4.36 mmol) in CH2Cl2 (20 mL). After stirring the reaction mixture for 8 h at
room temperature, the reaction mixture was poured into a saturated aqueous solution of sodium
bicarbonate and extracted with EtOAc. The organic layer was washed with a saturated aqueous solution
of sodium thiosulfate and a saturated aqueous solution of sodium chloride, successively, sodium sulfate,
and condensed in vacuo. The residue was purified by silica gel column chromatography (hexane:EtOAc =
1
5:1) and recrystallization (CHCl3hexane) to afford 5b (433.0 mg, 30%). mp 57-58 ºC. H-NMR
(CDCl3)1.21 (1H, br, OH), 1.31 (8H, m), 1.52-1.61 (4H, m), 2.54 (2H, t, J = 7.7 Hz), 3.63 (2H, br t, J
= 5.9 Hz), 6.92 (2H, d, J = 8.4 Hz), 7.58 (2H, d, J = 8.4 Hz). 13C-NMR (CDCl3): 25.7, 29.1, 29.3, 29.4,
31.2, 32.7, 35.4, 63.0, 90.5, 130.5 (2C), 137.2 (2C), 142.5. IR (CHCl3) : 3445, 3007, 2932, 2858, 1638,
1485, 1400, 1061, 1007 cm-1. HR-MS (EI+, 70eV) m/z: 332.0632 (Calcd for C14H21IO: 332.0637).
2-Trimethylsilylethyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-
O-acetyl--D-mannopyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (3)
Palladium hydroxide on carbon (127.4 mg) was added to a solution of 912,13 (247.0 mg, 0.20 mmol) in a

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HETEROCYCLES, Vol. 83, No. 12, 2011
mixed solvent of MeOH (6 mL) and EtOAc (4 mL), which was stirred under a hydrogen atomosphere for
21 h at room temperature. After the reaction, the reaction mixture was filtered and the filtrate was
condensed in vacuo. The residue was treated with pyridine (5 mL) and acetic anhydride (1 mL) for 32 h.
The mixture was poured into ice water, which was extracted with EtOAc. The organic layer was washed
with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate, and condensed in
vacuo. The residue was purified by silica gel column chromatography (hexane:EtOAc = 1:4) to afford 3
(180.4 mg, 87%, 2 steps). []D 8.5° (c 0.88, CHCl3). 1H-NMR (C5D5N)  0.05 (9H, s), 0.99 (1H, ddd, J
= 5.4, 9.1, 14.1 Hz), 1.09 (1H, ddd, J = 7.0, 9.8, 14.1 Hz), 1.97, 1.98, 2.01, 2.06, 2.07, and 2,08 (each 3H,
s), 2.088 (6H, s), 2.094 (3H, s), 2.10 (3H, s), 3.72-3.78 (2H, m, Glc-6, -OCH2), 4.01 (1H, ddd, J = 2.2, 5.7,
10.3 Hz, GlcN-5), 4.03-4.17 (3H, m, GlcN-2, Glc-5, Glc-6), 4.25-4.31 (1H, m, -OCH2), 4.27 (1H, dd, J =
2.2, 12.4 Hz, GlcN-6), 4.33-4.37 (1H, m, Man-5), 4.42 (1H, dd, J = 1.8, 12.1 Hz, Man-6), 4.53 (1H, dd, J
= 5.3, 12.1 Hz, Man-6), 4.61 (1H, dd, J = 5.7, 12.4 Hz, GlcN-6), 4.79 (1H, t, J = 1.7 Hz, Man-2), 4.95
(1H, d, J = 8.1 Hz, Glc-1), 5.27 (1H, s, Man-1), 5.41 (1H, t, J = 9.5 Hz, GlcN-4), 5.43 (1H, t, J = 9.3 Hz,
Glc-2), 5.46 (1H, t, J = 9.3 Hz, Glc-4), 5.54 (1H, d, J = 8.4 Hz, GlcN-1), 5.58 (1H, dd, J = 3.1, 10.3 Hz,
Man-3), 5.76 (1H, t, J = 9.3 Hz, Glc-3), 5.89 (1H, t, J = 10.3 Hz, Man-4), 6.04 (1H, t, J = 9.5 Hz, GlcN-3),
9.25 (1H, d, J = 8.1 Hz). 13C-NMR (C5D5N) : 1.32 (3C), 18.0, 20.47, 20.49, 20.52, 20.65, 20.67, 20.70,
20.8, 55.7 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.4 (Man-4), 67.3 (Glc-6), 67.6 (-OCH2), 69.6
(Man-5), 69.8 (GlcN-4), 70.1 (Glc-4), 71.0 (Man-3), 72.16 (Glc-2), 72.21 (GlcN-5), 72.6 (GlcN-3), 72.8
(Glc-5), 73.7 (Glc-3), 74.4 (Man-2), 98.4 (Man-1), 99.7 (GlcN-1), 100.5 (Glc-1), 169.6, 169.9, 170.0 (2C),
170.4, 170.47, 170.51, 170.6, 170.7, 171.0. IR (CHCl3) : 3030, 3015, 1751, 1682, 1514, 1429, 1367,
1256, 1138, 1040 cm-1. HR-MS (FAB+) m/z: 1046.3517 (Calcd for C43H65NO25SiNa: 1046.3513).
2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-O-acetyl--D-manno-
pyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranosyl trichloroacetimidate (4)
Triflouroacetic acid (300 L) was added to a solution of 3 (116.8 mg, 114.1 mol) in CH2Cl2 (3 mL),
which was stirred for 45 h at room temperature. The reaction mixture was poured into a saturated aqueous
solution of sodium bicarbonate, which was extracted with EtOAc. The organic layer was washed with a
saturated aqueous solution of sodium chloride, dried over sodium sulfate, and condensed in vacuo. The
residue was purified by silica gel chromatography (CHCl3:MeOH = 50:1) to give 2-acetamido-3,4,6-
tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-O-acetyl--D-mannopyranosyl-(1 → 6)-2,3,4-
tri-O-acetyl--D-glucopyranose trisaccharide (94.2 mg). Trichloroacetonitrile (102 L, 1.02 mmol) and
DBU (one drop with a pipet) were added to a solution of the trisaccharide (94.2 mg) in CH2Cl2 (3 mL),
which was stirred for 30 min at room temperature. The organic solvent was evaporated and the residue

HETEROCYCLES, Vol. 83, No. 12, 2011
2787
was purified by silica gel column chromatography (CHCl3:MeOH = 80:1) to afford 4 (84.2 mg, 69%, 2
1
steps). []D +36.5° (c 0.93, CHCl3). H-NMR (C5D5N)  1.96, 1.97, 1.98, 2.03, 2.05, 2.06, 2.08, 2.09,
2.11, and 2.15 (each 3H, s, OAc), 3.74 (1H, br d, J = 9.3 Hz, Glc-6), 4.01-4.03 (1H, m, GlcN-5),
4.07-4.14 (2H, m, GlcN-2, Glc-6), 4.25 (1H, dd, J = 1.5, 12.1 Hz, GlcN-6), 4.35-4.39 (1H, m, Man-5),
4.43 (1H, br d, J = 12.1 Hz, Man-6), 4.54-4.60 (3H, m, Glc-5, GlcN-6, Man-6), 4.79 (1H, br s, Man-2),
5.24 (1H, br s, Man-1), 5.41 (1H, t, J = 9.7 Hz, GlcN-4), 5.549 (1H, dd, J = 3.5, 10.4 Hz, Glc-2), 5.553
(1H, d, J = 9.0 Hz, GlcN-1), 5.57 (1H, dd, J = 3.7, 10.3 Hz, Man-3), 5.67 (1H, t, J = 9.9 Hz, Glc-4), 5.89
(1H, t, J = 10.3 Hz, Man-4), 6.04 (1H, t, J = 9.5 Hz, GlcN-3), 6.09 (1H, t, J = 9.9 Hz, Glc-3), 7.02 (1H, d,
J = 3.5 Hz, Glc-1), 9.22 (1H, d, J = 8.1 Hz), 10.26 (1H, s). 13C-NMR (C5D5N) : 20.3, 20.48, 20.50 (2C),
20.6 (3C), 20.7, 20.8, 23.2, 55.6 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.4 (Man-4), 66.9 (Glc-6), 69.0
(Glc-4), 69.5 (Man-5), 69.8 (GlcN-4), 70.5 (Glc-3), 70.6 (Glc-2), 71.0 (Man-3), 71.6 (Glc-5), 72.3
(GlcN-5), 72.7 (GlcN-3), 74.6 (Man-2), 79.8, 93.2 (Glc-1), 98.7 (Man-1), 100.0 (GlcN-1), 159.9, 169.87,
169.91, 170.0, 170.1, 170.3, 170.45, 170.49, 170.6, 170.8, 170.9. IR (CHCl3) : 3344, 3044, 3026, 3015,
1751, 1676, 1514, 1429, 1367, 1256, 1074, 1040 cm-1. HR-MS (FAB+) m/z: 1089.1898 (Calcd for
C40H53Cl3N2O25Na: 1089.1901).
2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-O-acetyl--D-manno-
pyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranosyl orthoester (11)
After stirring a suspension of 4 (34.6 mg, 32.4 mol), 5b (10.7 mg, 32.2 mol), and MS4A (150 mg) in
CH2Cl2 (2 mL) for 30 min, trimethylsilyl trifluoromethanesulfonate (0.6 L, 3.3 mol) was added to the
mixture chilled at 40 ºC. After stirring for 30 min. while maintaining the temperature, the reaction
mixture was filtered through Celite. The filtrate was partitioned between EtOAc and a saturated aqueous
solution of sodium bicarbonate. The organic layer was washed with a saturated aqueous solution of
sodium chloride, dried over magnesium sulfate, and condensed in vacuo. The residue was purified by
silica gel column chromatography (CHCl3: MeOH = 100:1) to afford 11 (6.0 mg, 15%). []D +15.1° (c
0.44, CHCl3). 1H-NMR (C5D5N) : 1.18 (6H, m), 1.28 (2H, m), 1.45-1.57 (4H, m), 1.88, 1.97, 1.98, 1.99,
2.06, 2.07, 2.088, and 2.093 (each 3H, s), 2.10 (6H, s), 2.44 (2H, t, J = 7.9 Hz), 3.55 (2H, t, J = 6.6 Hz,
-OCH2), 3.81 (1H, dd, J = 3.0, 10.9 Hz, Glc-6), 3.91 (1H, ddd, J = 2.2, 5.3, 10.1 Hz, GlcN-5), 4.06 (1H,
dt, J = 8.1, 10.4 Hz, GlcN-2), 4.15 (1H, dd, J = 4.9, 10.9 Hz, Glc-6), 4.22 (1H, dd, J = 2.2, 12.1 Hz,
GlcN-6), 4.31-4.35 (1H, m, Glc-5), 4.43-4.48 (1H, m, Man-5), 4.48 (1H, dd, J = 2.4, 12.2 Hz, Man-6),
4.54 (1H, dd, J = 4.4, 12.2 Hz, Man-6), 4.56 (1H, dd, J = 5.3, 12.1 Hz, GlcN-6), 4.77 (1H, dd, J = 1.5, 3.3
Hz, Man-2), 4.81 (1H, dd, J = 3.1, 5.1 Hz, Glc-2), 5.32 (1H, d, J = 1.5 Hz, Man-1), 5.40 (1H, t, J = 9.7 Hz,
GlcN-4), 5.49-5.52 (1H,, m, Glc-4), 5.51 (1H, d, J = 8.4 Hz, GlcN-1), 5.58 (1H, dd, J = 3.3, 10.3 Hz,

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HETEROCYCLES, Vol. 83, No. 12, 2011
Man-3), 5.66 (1H, t, J = 2.8 Hz, Glc-3), 5.90 (1H, t, J = 10.3 Hz, Man-4), 6.04 (1H, t, J = 9.7 Hz, GlcN-3),
6.17 (1H, d, J = 5.1 Hz, Glc-1), 6.96 (2H, br d, J = 8.2 Hz), 7.71 (2H, br d, J = 8.2 Hz), 9.25 (1H, d, J =
8.1 Hz). 13C-NMR (C5D5N) : 20.48, 20.52, 20.58, 20.61, 20.65, 20.70, 20.8 (2C), 21.6, 23.2, 26.4, 29.3,
29.5, 29.6, 30.0, 31.5, 35.4, 55.7 (GlcN-2), 62.6 (GlcN-6), 63.0 (Man-6), 63.5 (-OCH2), 66.4 (Man-4),
68.1 (Glc-6), 68.7 (Glc-5), 68.8 (Glc-4), 69.5 (Man-5), 69.8 (GlcN-4), 70.6 (Glc-3), 71.0 (Man-3), 72.2
(GlcN-5), 72.6 (GlcN-3), 73.6 (Glc-2), 74.8 (Man-2), 91.5, 97.6 (Glc-1), 98.7 (Man-1), 100.0 (GlcN-1),
122.2, 131.1 (2C), 137.7 (2C), 142.9, 169.6, 169.9, 170.0, 170.1, 170.47, 170.51, 170.6, 170.7, 171.0. IR
(CHCl3) : 3024, 2361, 1747, 1684, 1514, 1369, 1248, 1140, 1099 cm-1. HR-MS (FAB+) m/z: 1260.3325
(Calcd for C52H72INO25Na: 1260.3336).
p-Octyloxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthaloylamino--D-glucopyranosyl-(1 → 2)-3-O-
benzyl-4,6-O-benzylidene-1-thio--D-mannopyranoside (13)
A solution of triphenylphosphine (165.5 mg, 0.63 mmol) in CCl4 (2 mL) was added to a solution of 1214
(127.7 mg, 0.13 mmol) in MeCN (3 mL), which was stirred for 2 h under refluxing conditions. After the
reaction, the reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate and
extracted with EtOAc. The organic layer was washed with a saturated aqueous solution of sodium
chloride, dried over magnesium sulfate, and condensed in vacuo. The residue was purified by silica gel
column chromatography (hexane:EtOAc = 2:1) to afford 13 (115.2 mg, 92%). []D +131.1° (c 0.86,
1
CHCl3). H-NMR (C5D5N)  0.85 (3H, t, J = 7.1 Hz), 1.24 (8H, m), 1.42 (2H, m), 1.75 (2H, quint., J =
6.4 Hz), 1.84, 1.99, 2.01 (each 3H, s, OAc), 3.38 (1H, t, J = 9.9 Hz, Man-6), 3.87 (1H, dd, J = 4.2, 10.3
Hz, Man-6), 3.94 (2H, t, J = 6.4 Hz, OCH2), 4.19 (1H, ddd, J = 2.4, 4.6, 10.1 Hz, GlcN-5), 4.21 (1H, dd, J
= 2.8, 9.5 Hz, Man-3), 4.37 (1H, t, J = 9.5 Hz, Man-4), 4.37-4.42 (1H, m, Man-5), 4.42 (1H, dd, J = 4.6,
12.5 Hz, GlcN-6), 4.60 (1H, dd, J = 2.4, 12.5 Hz, GlcN-6), 4.78 (1H, d, J = 11.5 Hz, OBn), 4.98 (1H, dd,
J = 8.6, 10.8 Hz, GlcN-2), 5.00 (1H, d, J = 11.5 Hz, OBn), 5.02 (1H, br t, J = 2.8 Hz, Man-2), 5.57 (1H, s,
PhCH<), 5.61 (1H, dd, J = 9.2, 10.1 Hz, GlcN-4), 5.71 (1H, d, J = 1.7 Hz, Man-1), 6.23 (1H, d, J = 8.6
Hz, GlcN-1), 6.47 (1H, dd, J = 9.2, 10.8 Hz, GlcN-3), 7.02 (2H, d, J = 9.0 Hz), 7.26 (1H, tt, J = 1.3, 7.3
Hz), 7.29-7.36 (7H, m), 7.54-7.56 (2H, m), 7.61 (2H, br d, J = 8.4 Hz), 7.77 (1H, br), 7.88 (1H, br).
13C-NMR (C5D5N) : 14.3, 20.3, 20.4, 20.6, 22.9, 26.3, 29.48, 29.51, 29.6, 32.0, 55.4 (GlcN-2), 62.6
(GlcN-6), 65.5 (Man-5), 68.4 (OCH2), 68.5 (Man-6), 69.7 (GlcN-4), 71.0 (GlcN-3), 71.2 (OBn), 72.5
(GlcN-5), 75.0 (Man-3), 76.7 (Man-2), 78.9 (Man-4), 87.5 (Man-1), 96.7 (GlcN-1), 102.2 (PhCH<),
115.8 (2C), 123.6, 124.2 (6C), 126.9 (2C), 127.9, 128.4, 128.6 (2C), 129.2, 132.0, 134.0 (2C), 134.6,
138.5, 139.0, 159.7, 169.8, 170.4, 170.5. IR (CHCl3) : 2930, 1749, 1719, 1595, 1495, 1387, 1367, 1248,
1099 cm-1. HR-MS (FAB+) m/z: 1018.3663 (Calcd for C54H61NO15SNa: 1018.3660).

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2789
p-Octyloxyphenyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1→2)-3-O-benzyl-
4,6-O-benzylidene-1-thio--D-mannopyranoside (14)
Hydrazine hydrate (80% in water, 3 mL) was added to a solution of 13 (1.52 g, 1.53 mmol) in a mixed
solvent of EtOH (30 mL) and toluene (15 mL), which was stirred for 5 h under refluxing conditions. After
chilling the reaction mixture at room temperature, the resulting precipitates were filtered off. The filtrate
was condensed in vacuo and the residue was treated with pyridine (20 mL) and acetic anhydride (7 mL)
for 5 h. The mixture was poured into ice water, which was extracted with CHCl3. The organic layer was
dried over sodium sulfate and condensed in vacuo. The residue was purified by silica gel column
chromatography (CHCl3: EtOAc = 10:1) to afford 14 (1.19 g, 86%). []D +70.5° (c 1.21, CHCl3).
1H-NMR (C5D5N)  0.84 (3H, t, J = 7.1 Hz), 1.22 (8H, m), 1.40 (2H, m), 1.73 (2H, quint., J = 6.6 Hz),
1.96, 1.98, 2.00, and 2.04 (each 3H, s, Ac), 3.94 (2H, t, J = 6.6 Hz, OCH2), 3.98 (1H, t, J = 10.1 Hz,
Man-6), 4.02 (1H, ddd, J = 2.4, 4.9, 9.7 Hz, GlcN-5), 4.356 (1H, dd, J = 3.3, 9.7 Hz, Man-3), 4.361 (1H,
dd, J = 2.4, 12.3 Hz, GlcN-6), 4.43 (1H, dd, J = 4.6, 10.1 Hz, Man-6), 4.52 (1H, dt, J = 8.4, 10.6 Hz,
GlcN-2), 4.53 (1H, dd, J = 4.9, 12.3 Hz, GlcN-6), 4.66 (1H, t, J = 9.5 Hz, Man-4), 4.74 (1H, dt, J = 4.6,
9.5 Hz, Man-5), 4.84 (1H, d, J = 11.7 Hz, OBn), 5.04 (1H, t, J = 1.5 Hz, Man-2), 5.07 (1H, d, J = 11.7 Hz,
OBn), 5.49 (1H, t, J = 9.7 Hz, GlcN-4), 5.60 (1H, d, J = 8.4 Hz, GlcN-1), 5.66 (1H, s, PhCH<), 5.97 (1H,
dd, J = 9.3, 10.6 Hz, GlcN-3), 6.00 (1H, d, J = 1.5 Hz, Man-1), 7.03 (2H, d, J = 8.8 Hz), 7.25 (1H, tt, J =
1.3, 7.3 Hz), 7.30-7.40 (5H, m), 7.55 (2H, d, J = 8.8 Hz), 7.63 (2H, br d, J = 7.1 Hz), 7.68 (2H, br d, J =
13
8.4 Hz), 9.25 (1H, d, J = 8.6 Hz). C-NMR (C5D5N) : 14.2, 20.5, 20.57, 20.58, 22.9, 23.3, 26.3, 29. 5
(2C), 29.6, 32.0, 55.4 (GlcN-2), 62.7 (GlcN-6), 65.9 (Man-5), 68.4 (OCH2), 68.9 (Man-6), 69.7 (GlcN-4),
71.1 (OBn), 72.3 (GlcN-5), 73.0 (GlcN-3), 75.4 (Man-3), 76.7 (Man-2), 78.9 (Man-4), 88.1 (Man-1), 99.9
(GlcN-1), 102.2 (PhCH<), 115.9 (2C), 123.9, 126.9 (2C), 127.8, 128.3 (2C), 128.5 (2C), 128.6 (2C),
129.2, 135.5 (2C), 138.6, 139.2, 160.1, 169.8, 170.5, 170.7, 170.9. IR (CHCl3) : 3460, 3429, 2930, 2858,
1747, 1682, 1593, 1495, 1369, 1248, 1099 cm-1. HR-MS (FAB+) m/z: 930.3716 (Calcd for
C48H61NO14SNa: 930.3710).
p-Octyloxyphenyl 2-acetamido-3,4,6-tri-O-acetyl-2-doexy--D-glucopyranosyl-(1→2)-3-O-benzyl-1-
thio--D-mannopyranoside (15)
An aqueous solution of acetic acid (70%, 2 mL) was added to a solution of 14 (104.3 mg, 0.11 mmol) in
THF (1 mL), it was stirred for 5 h at 55 ºC. After neutralizing the mixture with an aqueous solution of
sodium bicarbonate, the mixture was extracted with CHCl3. The organic layer was washed with a
saturated aqueous solution of sodium bicarbonate, dried over sodium sulfate, and condensed in vacuo.
The residue was purified by silica gel column chromatography (CHCl3: MeOH = 30:1) to afford 15 (81.1

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1
mg, 86%). []D +17.4° (c 1.12, CHCl3). H-NMR (C5D5N + D2O)  0.84 (3H, t, J = 7.1 Hz), 1.21 (8H,
m), 1.39 (2H, m), 1.72 (2H, quint., J = 6.6 Hz), 1.97, 1.987, 1.990 and 2.03 (each 3H, s, Ac), 3.88, 3.91
(each 1H, dt, AB type, J = 6.6, 9.2 Hz, OCH2), 4.01 (1H, ddd, J = 2.4, 4.9, 9.7 Hz, GlcN-5), 4.27 (1H, dd,
J = 2.9, 9.2 Hz, Man-3), 4.35 (1H, dd, J = 2.4, 12.1 Hz, GlcN-6), 4.407 (1H, q, J = 8.6 Hz, GlcN-2),
4.412 (1H, dd, J = 5.5, 11.9 Hz, Man-6), 4.53 (1H, dd, J = 1.8, 11.9 Hz, Man-6), 4.55 (1H, dd, J = 4.9,
12.1 Hz, GlcN-6), 4.72 (1H, t, J = 9.2 Hz, Man-4), 4.77 (1H, d, J = 11.0 Hz, OBn), 4.85 (1H, ddd, J = 1.8,
5.5, 9.7 Hz, Man-5), 5.02 (1H, br t, J = 2.9 Hz, Man-2), 5.17 (1H, d, J = 11.0 Hz, OBn), 5.39 (1H, t, J =
9.7 Hz, GlcN-4), 5.54 (1H, d, J = 8.4 Hz, GlcN-1), 5.94 (1H, dd, J = 9.3, 10.6 Hz, GlcN-3), 6.06 (1H, d, J
= 1.7 Hz, Man-1), 7.02 (2H, d, J = 9.0 Hz), 7.29 (1H, tt, J = 1.3, 7.3 Hz), 7.35 (2H, br t, J = 7.0 Hz), 7.67
13
(2H, br d, J = 7.0 Hz), 7.78 (2H, d, J = 9.0 Hz), 9.29 (1H, d, J = 8.6 Hz). C-NMR (C5D5N) : 14.2,
20.47, 20.52, 20.6, 22.9, 23.3, 26.3, 29.45 (2C), 29.54, 32.0, 55.2 (GlcN-2), 62.8 (GlcN-6), 62.9 (Man-6),
67.0 (Man-4), 68.3 (OCH2), 69.8 (GlcN-4), 70.8 (OBn), 72.2 (GlcN-5), 72.9 (GlcN-3), 76.2 (Man-2),
76.6 (Man-5), 79.6 (Man-3), 87.9 (Man-1), 100.2 (GlcN-1), 115.7 (2C), 125.3, 127.8, 128.5 (2C), 128.8
(2C), 135.3 (2C), 139.4, 159.8, 169.8, 170.5, 170.6, 171.3. IR (CHCl3) : 3458, 3423, 3350, 2930, 2858,
1746, 1682, 1595, 1495, 1369, 1248, 1105, 1072 cm-1. HR-MS (FAB+) m/z: 842.3395 (Calcd for
C41H57NO14SNa: 842.3397).
p-Octyloxyphenyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-1-thio--D-
mannopyranoside (16)
Trimethylsilyl chloride (1.2 mL, 9.50 mmol) and lithium iodide (1.27 g, 9.50 mmol) were added to a
solution of 15 (817.2 mg, 0.95 mmol) in CHCl3 (15 mL) at 0 ºC. After stirring the reaction mixture for 6 h
at room temperature, it was poured into a saturated aqueous solution of sodium bicarbonate and extracted
with CHCl3. The organic layer was washed with a saturated aqueous solution of sodium thiosulfate and a
saturated aqueous solution of sodium chloride, dried over sodium sulfate, and condensed in vacuo. The
residue was purified by silica gel column chromatography (CHCl3: MeOH = 30:1) to afford 16 (662.5 mg,
1
96%). []D +37.4° (c 1.13, CHCl3). H-NMR (C5D5N + D2O)  0.84 (3H, t, J = 7.1 Hz), 1.20 (8H, m),
1.38 (2H, m), 1.70 (2H, quint., J = 6.6 Hz), 1.97, 1.98, 1.99, 2.03 (each 3H, s, Ac), 3.86, 3.88 (each 1H, dt,
J = 6.6, 9.5 Hz, OCH2), 3.96 (1H, ddd, J = 2.4, 4.8, 10.1 Hz, GlcN-5), 4.26 (1H, dd, J = 2.4, 12.3 Hz,
GlcN-6), 4.39 (1H, dt, J = 8.8, 10.8 Hz, GlcN-2), 4.41 (1H, dd, J = 5.9, 11.9 Hz, Man-6), 4.516 (1H, dd, J
= 4.8, 12.3 Hz, GlcN-6), 4.522 (1H, dd, J = 3.3, 9.2 Hz, Man-3), 4.55 (1H, dd, J = 2.2, 11.9 Hz, Man-6),
4.62 (1H, t, J = 9.3 Hz, Man-4), 4.86 (1H, ddd, J = 2.2, 5.9, 9.3 Hz, Man-5), 4.92 (1H, dd, J = 1.7, 3.3 Hz,
Man-2), 5.37 (1H, t, J = 9.3 Hz, GlcN-4), 5.51 (1H, d, J = 8.4 Hz, GlcN-1), 5.89 (1H, dd, J = 9.3, 10.8 Hz,
GlcN-3), 6.04 (1H, d, J = 1.7 Hz, Man-1), 6.97, 7.74 (each 2H, d, J = 8.8 Hz), 9.30 (1H, d, J = 8.8 Hz).

HETEROCYCLES, Vol. 83, No. 12, 2011
2791
13C-NMR (C5D5N) : 14.2, 20.46, 20.54, 20.6, 22.9, 23.3, 26.3, 29.45 (2C), 29.54, 32.0, 55.1 (GlcN-2),
62.5 (GlcN-6), 62.9 (Man-6), 68.3 (OCH2), 69.2 (Man-4), 69.6 (GlcN-4), 72.2 (GlcN-5), 72.5 (Man-3),
73.1 (GlcN-3), 76.8 (Man-5), 80.4 (Man-2), 88.0 (Man-1), 100.1 (GlcN-1), 115.6 (2C), 125.3, 135.3 (2C),
159.8, 169.8, 170.5, 170.6, 171.1. IR (CHCl3) : 3423, 3040, 2930, 2856, 1751, 1680, 1595, 1495, 1369,
1248, 1099, 1070 cm-1. HR-MS (FAB+) m/z: 752.2932 (Calcd for C34H51NO14SNa: 752.2928).
p-Octyloxyphenyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-O-
acetyl-1-thio--D-mannopyranoside (7)
Acetic anhydride (27 L, 0.29 mmol) and 4-dimethylaminopyridine (cat.) were added to a solution of 16
(50.9 mg, 69.7 mol) in pyridine (3 mL) at 0 ºC. After stirring the reaction mixture for 2 h at room
temperature, it was extracted with EtOAc. The organic layer was washed with a saturated solution of
sodium chloride, dried over magnesium sulfate, and condensed in vacuo. The residue was purified by
silica gel column chromatography (CHCl3: EtOAc = 3:2) to afford 7 (53.7 mg, 90%). []D +37.7° (c 0.92,
1
CHCl3). H-NMR (C5D5N)  0.83 (3H, t, J = 7.0 Hz), 1.22 (8H, m), 1.40 (2H, m), 1.73 (2H, quint., J =
6.6 Hz), 1.95, 1.97, 1.98, 2.092, 2.094, 2.11, 2.12 (each 3H, s, Ac), 3.94 (2H, t, J = 6.6 Hz, OCH2), 3.97
(1H, ddd, J = 2.4, 5.5, 10.1 Hz, GlcN-5), 4.20-4.27 (1H, m, GlcN-2), 4.25 (1H, dd, J = 2.4, 12.5 Hz,
GlcN-6), 4.41 (1H, dd, J = 2.2, 12.1 Hz, Man-6), 4.56 (1H, dd, J = 5.5, 12.5 Hz, GlcN-6), 4.61 (1H, dd, J
= 6.0, 12.1 Hz, Man-6), 4.88 (1H, ddd, J = 2.2, 6.0, 9.7 Hz, Man-5), 5.10 (1H, br dd, J = 1.7, 3.1 Hz,
Man-2), 5.41 (1H, t, J = 9.5 Hz, GlcN-4), 5.54 (1H, dd, J = 3.1, 10.1 Hz, Man-3), 5.62 (1H, d, J = 8.4 Hz,
GlcN-1), 5.88 (1H, br s, Man-1), 5.94 (1H, t, J = 10.1 Hz, Man-4), 5.97 (1H, t, J = 9.7 Hz, GlcN-3), 7.05
(2H, d, J = 8.8 Hz), 7.59 (2H, d, J = 8.8 Hz), 9.21 (1H, d, J = 8.2 Hz). 13C-NMR (C5D5N) : 14.2, 20.46,
20.50, 20.6, 20.65, 20.69, 20.8, 22.9, 23.1, 26.3, 29.45 (2C), 29.54, 32.0, 55.3 (GlcN-2), 62.6 (GlcN-6),
63.1 (Man-6), 66.8 (Man-4), 68.4 (OCH2), 69.7 (GlcN-4), 70.2 (Man-5), 71.4 (Man-3), 72.2 (GlcN-5),
72.8 (GlcN-3), 76.1 (Man-2), 87.3 (Man-1), 99.7 (GlcN-1), 115.7 (2C), 124.0, 135.3 (2C), 160.2, 169.8,
170.0, 170.55 (2C), 170.61, 170.7, 170.9. IR (CHCl3) : 3042, 2930, 2856, 1746, 1684, 1595, 1495, 1369,
1250, 1057 cm-1. HR-MS (FAB+) m/z: 878.3249 (Calcd for C40H57NO17SNa: 878.3245).
2-(p-Iodophenyl)ethyl 2,3,4-tri-O-acetyl-6-O-allyloxycarbonyl--D-glucopyranoside (18a)
.
BF3 Et2O (21 L, 0.17 mmol) was added to a solution of 1711 (524.5 mg, 0.98 mmol) and 5a (203.2 mg,
0.82 mmol) in CH2Cl2 (12 mL) at 20 ºC. After stirring the reaction mixture for 4 h, it was poured into a
saturated aqueous solution of sodium bicarbonate and extracted with CHCl3. The organic layer was dried
over sodium sulfate and condensed in vacuo. The residue was purified by silica gel column
chromatography (hexane: EtOAc = 3:1) to afford 18a (315.9 mg, 62%). []D 13.4° (c 0.96, CHCl3).

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1H-NMR (C5D5N)  1.969, 1.971, 2.01 (each 3H, s, OAc), 2.74 (1H, dt, J = 6.2, 13.8 Hz), 2.78 (1H, dt, J
= 6.6, 13.8 Hz), 3.71 (1H, ddd, J = 6.6, 7.5, 9.5 Hz), 4.12 (1H, dt, J = 6.2, 9.5 Hz), 4.17 (1H, ddd, J = 2.9,
4.9, 10.1 Hz, H-5), 4.56 (1H, dd, J = 2.9, 11.9 Hz, H-6), 4.61 (1H, dd, J = 4.9, 11.9 Hz, H-6), 4.66 (2H, br
dt, J = 1.7, 5.7 Hz), 4.90 (1H, d, J = 8.1 Hz, H-1), 5.15 (1H, qd, J = 1.3, 10.4 Hz), 5.31 (1H, qd, J = 1.7,
17.2 Hz), 5.42 (1H, dd, J = 8.1, 9.7 Hz, H-2), 5.49 (1H, t, J = 9.5 Hz, H-4), 5.71 (1H, t, J = 9.5 Hz, H-3),
13
5.91 (1H, ddt, J = 5.7, 10.4, 17.2 Hz), 6.96 (1H, d, J = 8.4 Hz), 7.66 (1H, d, J = 8.4 Hz). C-NMR
(C5D5N) : 20.4, 20.46, 20.52, 35.6, 66.3 (C-6), 68.8, 69.3 (C-4), 70.1, 71.8 (C-2), 72.1 (C-5), 73.3 (C-3),
92.3, 101.0 (C-1), 118.6, 131.6 (2C), 132.3, 137.6 (2C), 139.0, 155.2, 169.5, 169.9, 170.3. IR (CHCl3) :
3038, 3013, 1755, 1603, 1366, 1242, 1063 cm-1. HR-MS (FAB+) m/z: 643.0649 (Calcd for C24H29O11INa:
643.0652).
8-(p-Iodophenyl)octyl 2,3,4-tri-O-acetyl-6-O-allyloxycarbonyl--D-glucopyranoside (18b)
.
BF3 Et2O (24 L, 0.19 mmol) was added to a solution of 1711 (604.1 mg, 1.13 mmol) and 5b (311.2 mg,
0.94 mmol) in CH2Cl2 (12 mL) at 20 ºC. After stirring the reaction mixture for 4 h, it was treated in the
same manner as the synthesis of 18a. The residue was purified by silica gel column chromatography
(hexane: EtOAc = 4:1) to afford 18b (417.1 mg, 63%). []D 9.8° (c 1.22, CHCl3). 1H-NMR (C5D5N) 
1.16 (6H, m), 1.26 (2H, m), 1.43-1.58 (4H, m), 1.99, 2.03, 2.08 (each 3H, s, OAc), 2.44 (2H, t, J = 7.9
Hz), 3.55 (1H, dt, J = 6.6, 9.7 Hz, OCH2), 3.93 (1H, dt, J = 6.4, 9.7 Hz, OCH2), 4.20 (1H, ddd, J = 2.9,
4.9, 10.1 Hz, H-5), 4.57 (1H, dd, J = 2.9, 11.9 Hz, H-6), 4.63 (1H, dd, J = 4.9, 11.9 Hz, H-6), 4.67 (2H, br
dt, J = 5.7, 1.5 Hz), 4.93 (1H, d, J = 7.9 Hz, H-1), 5.15 (1H, qd, J = 1.3, 10.4 Hz), 5.32 (1H, qd, J = 1.5,
17.2 Hz), 5.46 (1H, dd, J = 7.9, 9.9 Hz, H-2), 5.51 (1H, t, J = 9.5 Hz, H-4), 5.77 (1H, t, J = 9.5 Hz, H-3),
13
5.92 (1H, ddt, J = 17.2, 10.4, 5.7 Hz) , 6.97 (2H, d, J = 8.4 Hz), 7.71 (2H, d, J = 8.4 Hz). C-NMR
(C5D5N) : 20.45, 20.48, 20.6, 26.1, 29.3, 29.4, 29.6, 29.8, 31.5, 35.5, 66.4 (C-6), 68.8, 69.4 (C-4), 70.1,
72.06 (C-2), 72.09 (C-5), 73.4 (C-3), 91.4, 101.1 (C-1), 118.6, 131.1 (2C), 132.3, 137.7 (2C), 142.9,
155.2, 169.5, 169.9, 170.3. IR (CHCl3) : 2934, 2856, 1755, 1367, 1248, 1065 cm-1. HR-MS (FAB+) m/z:
727.1594 (Calcd for C30H41O11INa: 727.1591).
15-(p-Iodophenyl)pentadecyl 2,3,4-tri-O-acetyl-6-O-allyloxycarbonyl--D-glucopyranoside (18c)
.
BF3 Et2O (16 L, 0.13 mmol) was added to a solution of 1711 (278.0 mg, 0.64 mmol) and 5c (414.0 mg,
0.77 mmol) in CH2Cl2 (12 mL) at 20 ºC. After stirring the reaction mixture for 2.5 h, it was treated in
the same manner as the synthesis of 18a. The residue was purified by silica gel column chromatography
1
(hexane: EtOAc = 4:1 to 3:1) to afford 18c (369 mg, 71%). []D 6.9° (c 1.18, CHCl3). H-NMR
(C5D5N)  1.22-1.31 (22H, m), 1.50-1.59 (4H, m), 1.99, 2.03, 2.09 (each 3H, s, OAc), 2.47 (2H, t, J =

HETEROCYCLES, Vol. 83, No. 12, 2011
2793
7.9 Hz), 3.56 (1H, dt, J = 6.7, 9.6 Hz, OCH2), 3.95 (1H, dt, J = 6.4, 9.6 Hz, OCH2), 4.20 (1H, ddd, J = 2.8,
4.9, 10.1 Hz, H-5), 4.57 (1H, dd, J = 2.8, 11.9 Hz, H-6), 4.62 (1H, dd, J = 4.9, 11.9 Hz, H-6), 4.67 (2H, br
dt, J = 1.5, 5.7 Hz), 4.93 (1H, d, J = 8.1 Hz, H-1), 5.16 (1H, qd, J = 1.3, 10.4 Hz), 5.33 (1H, qd, J = 1.5,
17.2 Hz), 5.46 (1H, dd, J = 8.1, 9.7 Hz, H-2), 5.50 (1H, dd, J = 9.5, 10.1 Hz, H-4), 5.76 (1H, t, J = 9.5 Hz,
H-3), 5.93 (1H, ddt, J = 17.2, 10.4, 5.7 Hz) , 6.98 (2H, d, J = 8.4 Hz), 7.71 (2H, d, J = 8.4 Hz). 13C-NMR
(C5D5N) : 20.45, 20.48, 20.6, 26.1, 29.4, 29.6, 29.7, 29.8, 29.86, 29.89 (2C), 30.0 (4C), 31.5, 35.5, 66.4
(C-6), 68.8, 69.4 (C-4), 70.1, 72.07 (C-2), 72.09 (C-5), 73.4 (C-3), 91.5, 101.1 (C-1), 118.6, 131.1 (2C),
132.3, 137.7 (2C), 143.0, 155.2, 169.5, 169.9, 170.3. IR (CHCl3) : 2928, 2855, 1755, 1367, 1248, 1065
cm-1. HR-MS (FAB+) m/z: 825.2695 (Calcd for C37H55O11INa: 825.2687).
2-(p-Iodophenyl)ethyl 2,3,4-tri-O-acetyl--D-glucopyranoside (8a)
Tetrakis(triphenylphosphine)palladium(0) (12.4 mg, 10.7 mol), triphenylphosphine (16.9 mg, 64.4
mol), and formic acid (16.5 L, 0.43 mmol) were added to a solution of 18a (133.0 mg, 0.21 mmol) in
THF (5 mL). After stirring the reaction mixture for 1 h, it was extracted with EtOAc, washed with
distilled water and a saturated aqueous solution of sodium chloride, successively, dried over sodium
sulfate, and condensed in vacuo. The residue was purified by silica gel column chromatography (hexane:
1
EtOAc = 1:1) to afford 8a (109.0 mg, 95%). []D 31.0° (c 0.91, CHCl3). H-NMR (C5D5N)  1.98,
1.985, 1.990 (each 3H, s, OAc), 2.72 (1H, dt, J = 6.0, 13.9 Hz), 2.76 (1H, dt, J = 7.5, 13.9 Hz), 3.68 (1H,
ddd, J = 6.4, 7.5, 9.7 Hz), 3.96-4.03 (2H, m, H-5 and H-6), 4.08 (1H, dt, J = 6.0, 9.7 Hz), 4.10-4.14 (1H,
m, H-6), 4.88 (1H, d, J = 8.1 Hz, H-1), 5.44 (1H, dd, J = 8.1, 9.5 Hz, H-2), 5.63 (1H, t, J = 9.5 Hz, H-4),
13
5.72 (1H, t, J = 9.5 Hz, H-3), 6.94 (2H, d, J = 8.4 Hz), 7.66 (2H, d, J = 8.4 Hz). C-NMR (C5D5N) :
20.5, 20.56, 20.58, 35.6, 61.3 (C-6), 69.7 (C-4), 70.0, 72.1 (C-2), 74.0 (C-3), 75.6 (C-5), 92.3, 101.0 (C-1),
131.6 (2C), 137.6 (2C), 139.0, 169.6, 169.8, 170.4. IR (CHCl3) : 3570, 3030, 3022, 3015, 1755, 1485,
1367, 1254, 1088, 1063, 1040 cm-1. HR-MS (FAB+) m/z: 559.0447 (Calcd for C20H25O9INa: 559.0441).
8-(p-Iodophenyl)octyl 2,3,4-tri-O-acetyl--D-glucopyranoside (8b)
Tetrakis(triphenylphosphine)palladium(0) (16.0 mg, 13.8 mol), triphenylphosphine (21.9 mg, 83.5
mol), and formic acid (22 L, 0.57 mmol) were added to a solution of 18b (197.6 mg, 0.28 mmol) in
THF (6 mL). After stirring the reaction mixture for 1 h, it was treated in the same manner as the synthesis
of 8a. The residue was purified by silica gel column chromatography (hexane: EtOAc = 2:1) to afford 8b
1
(162.8 mg, 94%). []D 20.0° (c 0.91, CHCl3). H-NMR (C5D5N)  1.16 (6H, m), 1.24 (2H, m),
1.42-1.57 (4H, m), 2.00, 2.09 (6H and 3H, s, OAc), 2.44 (2H, t, J = 7.7 Hz), 3.53 (1H, dt, J = 6.7, 9.6 Hz),
3.91 (1H, dt, J = 6.4, 9.6 Hz), 3.99-4.05 (2H, m, H-5 and H-6), 4.13 (1H, br dt, J = 4.4, 9.6 Hz, H-6), 4.91

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(1H, d, J = 8.1 Hz, H-1), 5.48 (1H, dd, J = 8.1, 9.9 Hz, H-2), 5.65 (1H, t, J = 9.3 Hz, H-4), 5.77 (1H, t, J =
13
9.3 Hz, H-3), 6.97 (2H, d, J = 8.2 Hz), 7.71 (2H, d, J = 8.2 Hz). C-NMR (C5D5N) : 20.5, 20.6, 20.7,
26.1, 29.3, 29.4, 29.6, 29.8, 31.5, 35.5, 61.3 (C-6), 69.7 (C-4), 69.9, 72.3 (C-2), 74.1 (C-3), 75.6 (C-5),
91.5, 101.2 (C-1), 131.1 (2C), 137.7 (2C), 142.9, 169.6, 169.8, 170.4. IR (CHCl3) : 3595, 3026, 2932,
2858, 1755, 1485, 1369, 1254, 1040 cm-1. HR-MS (FAB+) m/z: 643.1384 (Calcd for C26H37O9INa:
643.1380).
15-(p-Iodophenyl)pentadecyl 2,3,4-tri-O-acetyl--D-glucopyranoside (8c)
Tetrakis(triphenylphosphine)palladium(0) (5.2 mg, 4.5 mol), triphenylphosphine (7.0 mg, 26.7 mol),
and formic acid (6.9 L, 0.18 mmol) were added to a solution of 18c (71.7 mg, 89.3 mol) in THF (3
mL). After stirring the reaction mixture for 1 h, it was treated in the same manner as the synthesis of 8a.
The residue was purified by silica gel column chromatography (hexane : EtOAc = 3:2) to afford 8c (61.7
1
mg, 96%). []D 17.1° (c 0.88, CHCl3). H-NMR (C5D5N)  1.22-1.30 (22H, m), 1.49-1.59 (4H, m),
2.00, 2.11 (6H and 3H, s, OAc), 2.47 (2H, t, J = 7.9 Hz), 3.55 (1H, dt, J = 6.7, 9.6 Hz), 3.92 (1H, dt, J =
6.4, 9.6 Hz), 3.99-4.05 (2H, m, H-5 and H-6), 4.14 (1H, br dt, J = 4.4, 9.9 Hz, H-6), 4.91 (1H, d, J = 8.1
Hz, H-1), 5.48 (1H, dd, J = 8.1, 9.7 Hz, H-2), 5.65 (1H, t, J = 9.5 Hz, H-4), 5.77 (1H, t, J = 9.5 Hz, H-3),
6.98 (2H, d, J = 8.1 Hz), 7.71 (2H, d, J = 8.1 Hz). 13C-NMR (C5D5N) : 20.5, 20.6, 20.7, 26.2, 29.4, 29.6,
29.7, 29.8, 29.86, 29.89 (2C), 30.0 (4C), 31.5, 35.5, 61.3 (C-6), 69.7 (C-4), 70.0, 72.4 (C-2), 74.1 (C-3),
75.6 (C-5), 91.5, 101.2 (C-1), 131.2 (2C), 137.7 (2C), 142.9, 169.6, 169.9, 170.4. IR (CHCl3) : 3543,
2928, 2855, 1755, 1603, 1369, 1254, 1088, 1038 cm-1. HR-MS (FAB+) m/z: 741.2471 (Calcd for
C33H51O9INa: 741.2476).
2-(p-Iodophenyl)ethyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-
O-acetyl--D-mannopyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (10a)
After stirring a suspension of 7 (166.0 mg, 0.19 mmol), 8a (87.5 mg, 0.16 mmol), and MS4A (300 mg) in
CH2Cl2 (5 mL) for 30 min, N-iodosuccinimide (91.8 mg, 0.41 mmol) and triflic acid (one drop with a
capillary) were added to a suspension at 50 ºC. After stirring the reaction mixture for 2 h while
maintaining the temperature, the reaction was quenched by filtering the mixture through Celite. The
filtrate was poured into a saturated aqueous solution of sodium bicarbonate, which was extracted with
EtOAc. The organic layer was washed with a saturated aqueous solution of sodium thiosulfate and a
saturated aqueous solution of sodium chloride, successively, dried over magnesium sulfate, and
condensed in vacuo. The residue was purified by silica gel column chromatography (CHCl3: EtOAc =
1
1:1) to afford 10a (161.8 mg, 86%). []D +20.1o (c 0.60, CHCl3). H-NMR (C5D5N)  1.96, 1.97, 1.98,

HETEROCYCLES, Vol. 83, No. 12, 2011
2795
1.99, 2.00, 2.06, 2.07, 2.09, 2.097 and 2.103 (each 3H, s), 2.88 (1H, dt, J = 6.0, 14.5 Hz), 2.94 (1H, dt, J =
7.1, 14.5 Hz), 3.75-3.83 (2H, m, -OCH2, Glc-6), 4.00-4.13 (4H, m, GlcN-2, GlcN-5, Glc-5, Glc-6), 4.28
(1H, dd, J = 2.2, 12.3 Hz, GlcN-6), 4.32-4.38 (2H, m, -OCH2, Man-5), 4.44 (1H, dd, J = 2.7, 12.1 Hz,
Man-6), 4.50 (1H, dd, J = 5.3, 12.1 Hz, Man-6), 4.63 (1H, dd, J = 5.5, 12.3 Hz, GlcN-6), 4.80 (1H, dd, J
= 1.3, 3.5 Hz, Man-2), 4.90 (1H, d, J = 8.1 Hz, Glc-1), 5.29 (1H, d, J = 1.3 Hz, Man-1), 5.40 (1H, dd, J =
8.1, 9.7 Hz, Glc-2), 5.42 (1H, t, J = 9.5 Hz, GlcN-4), 5.45 (1H, t, J = 9.5 Hz, Glc-4), 5.59 (1H, d, J = 8.6
Hz, GlcN-1), 5.61 (1H, dd, J = 3.5, 10.1 Hz, Man-3), 5.72 (1H, t, J = 9.5 Hz, Glc-3), 5.87 (1H, t, J = 10.1
Hz, Man-4), 6.09 (1H, dd, J = 9.5, 10.6 Hz, GlcN-3), 7.06 (2H, br d, J = 8.2 Hz), 7.71 (2H, br d, J = 8.2
Hz), 9.29 (1H, d, J = 8.1 Hz). 13C-NMR (C5D5N) : 20.4, 20.50, 20.52, 20.54, 20.57, 20.63, 20.66, 20.67,
20.8, 23.2, 35.7, 55.8 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.5 (Man-4), 67.1 (Glc-6), 69.6 (Glc-4),
69.87 (GlcN-4), 69.90 (Man-5), 70.5 (-OCH2), 70.9 (Man-3), 71.9 (Glc-2), 72.2 (GlcN-5), 72.6 (GlcN-3),
73.0 (Glc-5), 73.5 (Glc-3), 74.5 (Man-2), 92.3, 98.4 (Man-1), 99.6 (GlcN-1), 101.1 (Glc-1), 131.7 (2C),
137.7 (2C), 139.1, 169.5, 169.87, 169.91, 170.0, 170.3, 170.48, 170.54, 170.6, 170.7, 171.0. IR (CHCl3)
: 3024, 1753, 1680, 1601, 1367, 1240, 1040 cm-1. HR-MS (FAB+) m/z: 1176.2405 (Calcd for
C46H60INO25Na: 1176.2397).
8-(p-Iodophenyl)octyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-3,4,6-tri-
O-acetyl--D-mannopyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (10b)
After stirring a suspension of 7 (326.5 mg, 0.38 mmol), 8b (195.7 mg, 0.32 mmol), and MS4A (500 mg)
in CH2Cl2 (10 mL) for 30 min, N-iodosuccinimide (178.6 mg, 0.79 mmol) and triflic acid (one drop with
a capillary) were added to a suspension at 50 ºC. After stirring the reaction mixture for 2 h while
maintaining the temperature, the reaction mixture was treated in the same manner as the synthesis of 10a.
The residue was purified by silica gel column chromatography (CHCl3: EtOAc = 1:1) to afford 10b
(318.5 mg, 82%). []D 2.4o (c 0.99, CHCl3). 1H-NMR (C5D5N)  1.22-1.37 (8H, m), 1.47-1.68 (4H, m),
1.97, 1.99, 2.02, and 2.07 (each 3H, s), 2.09 (9H, s), 2.098, 2.103, and 2.11 (each 3H, s), 2.46 (2H, t, J =
7.9 Hz), 3.63 (1H, dt, J = 6.8, 9.7 Hz, -OCH2), 3.75-3.80 (1H, m, Glc-6), 4.01 (1H, ddd, J = 2.2, 5.5, 10.3
Hz, GlcN-5), 4.04-4.16 (4H, m, GlcN-2, Glc-5, Glc-6, -OCH2), 4.28 (1H, dd, J = 2.2, 12.2 Hz, GlcN-6),
4.38 (1H, ddd, J = 2.4, 5.1, 10.1 Hz, Man-5), 4.44 (1H, dd, J = 2.4, 12.1 Hz, Man-6), 4.53 (1H, dd, J =
5.1, 12.1 Hz, Man-6), 4.61 (1H, dd, J = 5.5, 12.2 Hz, GlcN-6), 4.79 (1H, dd, J = 1.5, 3.5 Hz, Man-2), 4.93
(1H, d, J = 8.1 Hz, Glc-1), 5.28 (1H, d, J = 1.5 Hz, Man-1), 5.41 (1H, t, J = 9.7 Hz, GlcN-4), 5.45 (1H, dd,
J = 8.1, 9.7 Hz, Glc-2), 5.46 (1H, t, J = 9.3 Hz, Glc-4), 5.54 (1H, d, J = 8.4 Hz, GlcN-1), 5.61 (1H, dd, J
= 3.5, 10.3 Hz, Man-3), 5.77 (1H, t, J = 9.7 Hz, Glc-3), 5.89 (1H, t, J = 10.3 Hz, Man-4), 6.05 (1H, t, J =
10.1 Hz, GlcN-3), 6.97 (2H, br d, J = 8.2 Hz), 7.71 (2H, br d, J = 8.2 Hz), 9.25 (1H, d, J = 8.2 Hz).

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13C-NMR (C5D5N) : 20.48, 20.50, 20.53, 20.7 (5C), 20.8, 23.2, 26.2, 29.4, 29.5, 29.7, 29.8, 31.5, 35.5,
55.8 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.5 (Man-4), 67.2 (Glc-6), 69.6 (Man-5), 69.8 (GlcN-4),
70.1 (Glc-4), 70.3 (-OCH2), 71.0 (Man-3), 72.18 (Glc-2), 72.23 (GlcN-5), 72.6 (GlcN-3), 72.9 (Glc-5),
73.6 (Glc-3), 74.5 (Man-2), 91.5, 98.4 (Man-1), 99.7 (GlcN-1), 101.1 (Glc-1), 131.1 (2C), 137.7 (2C),
142.9, 169.6, 169.9, 170.0 (2C), 170.4, 170.48, 170.54, 170.6, 170.7, 171.0. IR (CHCl3) : 3032, 3013,
2932, 2856, 2359, 2341, 1751, 1684, 1367, 1244, 1043 cm-1. HR-MS (FAB+) m/z: 1260.3341 (Calcd for
C52H72INO25Na: 1260.3336).
15-(p-Iodophenyl)pentadecyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1 → 2)-
3,4,6-tri-O-acetyl--D-mannopyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (10c)
After stirring a suspension of 7 (88.5 mg, 103.4 mol), 8c (61.7 mg, 85.9 mol), and MS4A (150 mg) in
CH2Cl2 (3 mL) for 30 min, N-iodosuccinimide (48.4 mg, 215.1 mol) and triflic acid (one drop with a
capillary) were added to a suspension at 50 ºC. After stirring the reaction mixture for 2 h while
maintaining the temperature, the reaction mixture was treated in the same manner as the synthesis of 10a.
The residue was purified by silica gel column chromatography (CHCl3: EtOAc = 1:1) to afford 10c (97.5
mg, 85%). []D 17.3o (c 1.10, CHCl3). 1H-NMR (C5D5N)  1.26 (20H, m), 1.37-1.40 (2H, m), 1.50-1.55
(2H, m), 1.59-1.70 (2H, m), 1.97, 1.99, 2.01, 2.07, 2.09 and 2.095 (each 3H, s), 2.099 (6H, s), 2.104
(3H,s), 2.104 (3H, s), 2.47 (2H, t, J = 7.9 Hz), 3.64 (1H, dt, J = 6.8, 9.7 Hz, -OCH2), 3.75-3.79 (1H, m,
Glc-6), 4.01 (1H, ddd, J = 2.2, 5.5, 10.1 Hz, GlcN-5), 4.05-4.16 (4H, m, -OCH2, GlcN-2, Glc-5, Glc-6),
4.28 (1H, dd, J = 2.2, 12.3 Hz, GlcN-6), 4.39 (1H, ddd, J = 2.4, 5.3, 10.1 Hz, Man-5), 4.45 (1H, dd, J =
2.4, 12.1 Hz, Man-6), 4.54 (1H, dd, J = 5.3, 12.1 Hz, Man-6), 4.62 (1H, dd, J = 5.5, 12.3 Hz, GlcN-6),
4.79 (1H, dd, J = 1.7, 3.5 Hz, Man-2), 4.93 (1H, d, J = 8.1 Hz, Glc-1), 5.33 (1H, d, J = 1.7 Hz, Man-1),
5.41 (1H, t, J = 9.3 Hz, GlcN-4), 5.45 (1H, dd, J = 8.1, 9.7 Hz, Glc-2), 5.46 (1H, t, J = 9.5 Hz, Glc-4),
5.54 (1H, d, J = 8.4 Hz, GlcN-1), 5.61 (1H, dd, J = 3.5, 10.3 Hz, Man-3), 5.77 (1H, t, J = 9.5 Hz, Glc-3),
5.90 (1H, t, J = 9.5 Hz, Glc-3), 6.05 (1H, dd, J = 9.3, 10.4 Hz, GlcN-3), 6.98 (2H, br d, J = 8.2 Hz), 7.71
(2H, br d, J = 8.2 Hz), 9.26 (1H, d, J = 8.1 Hz). 13C-NMR (C5D5N) : 20.47, 20.50, 20.53, 20.6 (5C), 20.8,
23.2, 26.3, 29.4, 29.67, 29.72, 29.86 (2C), 29.94 (2C), 30.0 (4C), 31.5, 35.5, 55.7 (GlcN-2), 62.7
(GlcN-6), 63.0 (Man-6), 66.5 (Man-4), 67.2 (Glc-2), 69.6 (Man-5), 69.8 (GlcN-4), 70.1 (Glc-4), 70.3
(-OCH2), 71.0 (Man-3), 72.17 (Glc-2), 72.22 (GlcN-5), 72.6 (GlcN-3), 72.9 (Glc-5), 73.6 (Glc-3), 74.5
(Man-2), 91.5, 98.3 (Man-1), 99.7 (GlcN-1), 101.1 (Glc-1), 131.1 (2C), 137.7 (2C), 143.0, 169.6, 169.9,
170.0 (2C), 170.4, 170.48, 170.54, 170.6, 170.7, 171.0. IR (CHCl3) : 3036, 2928, 2855, 2359, 1753,
1682, 1367, 1244, 1042 cm-1. HR-MS (FAB+) m/z: 1358.4437 (Calcd for C59H86INO25Na: 1358.4431).

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2-(p-Iodophenyl)ethyl 2-acetamido-2-deoxy--D-glucopyranosyl-(1→2)--D-mannopyranosyl-(1→6)-
-D-glucopyranoside (1a)
Sodium methoxide (28% in MeOH, 20 L) was added to a solution of 10a (30.1 mg, 26.1 mol) in
MeOH (2 mL), which was stirred for 30 min at room temperature. The reaction mixture was neutralized
with Dowex 50 (H+) (ca. 300 mg) and filtered. The filtrate was condensed in vacuo. The residue was
purified by a recycle HPLC on a reversed phase column (MeOH: H2O = 7:3) to afford 1a (15.9 mg, 79%).
[]D 27.3o (c 0.59, MeOH). 1H-NMR (C5D5N+D2O)  2.20 (3H, s), 2.90 (2H, t, J = 7.0 Hz), 3.82-3.90
(2H, m), 3.95-4.00 (2H, m), 4.05-4.12 (2H, m), 4.19-4.56 (13H, m), 4.64 (1H, t, J = 9.3 Hz), 4.80 (1H, d,
J = 7.7 Hz, Glc-1), 5.18 (1H, d, J = 7.1 Hz, GlcN-1), 5.53 (1H, br s, Man-1), 7.07 (2H, br d, J = 8.2 Hz),
7.61 (2H, br d, J = 8.2 Hz). 13C-NMR (C5D5N+D2O) : 23.6, 35.8, 57.8, 62.1, 62.7, 67.3, 68.5, 70.0, 71.2,
71.5, 71.9, 74.7, 75.0, 75.0, 75.3, 76.1, 78.2, 78.3, 79.4, 91.9, 98.5 (Man-1), 102.1 (GlcN-1), 104.4
(Glc-1), 131.7 (2C), 137.5 (2C), 139.2, 171.9. IR (KBr) : 3260, 2887, 2340, 1645, 1558, 1375, 1315,
1042 cm-1. HR-MS (FAB+) m/z: 798.1450 (Calcd for C28H42INO16Na: 798.1446).
8-(p-Iodophenyl)octyl 2-acetamido-2-deoxy--D-glucopyranosyl-(1 → 2)--D-mannopyranosyl-(1 →
6)--D-glucopyranoside (1b)
Sodium methoxide (28% in MeOH, 15 L) was added to a solution of 10b (19.1 mg, 15.4 mol) in
MeOH (1.5 mL), which was stirred for 30 min at room temperature. The reaction mixture was treated in
the same manner as the synthesis of 1a. The residue was purified by a recycle HPLC on a reversed phase
1
column (MeOH) to afford 1b (10.2 mg, 77%). []D 15.0o (c 0.41, MeOH). H-NMR (C5D5N+D2O) 
1.13 (6H, m), 1.31-1.45 (4H, m), 1.59-1.66 (2H, m), 2.19 (3H, s), 2.41 (2H, t, J = 7.9 Hz), 3.65 (1H, dt, J
= 6.7, 9.5 Hz), 3.88 (1H, ddd, J = 2.4, 5.1, 9.3 Hz), 3.96-4.02 (2H, m), 4.08-4.31 (7H, m), 4.35-4.55 (8H,
m), 4.63 (1H, t, J = 9.3 Hz), 4.79 (1H, d, J = 7.7 Hz, Glc-1), 5.12 (1H, d, J = 9.2 Hz, GlcN-1), 5.23 (1H,
13
br s, Man-1), 6.97 (2H, br d, J = 8.4 Hz), 7.70 (2H, br d, J = 8.4 Hz). C-NMR (C5D5N+D2O) : 23.8,
26.4, 29.3, 29.6, 29.7, 30.2, 31.5, 35.5, 57.9, 62.3, 62.9, 67.4, 68.8, 69.8, 71.5, 71.8, 72.1, 75.2, 75.3, 75.6,
76.3, 78.6, 78.7, 80.1, 91.4, 98.9 (Man-1), 102.6 (GlcN-1), 104.7 (Glc-1), 131.1 (2C), 137.6 (2C), 143.0,
171.6. IR (KBr) : 3231, 2926, 1638, 1040 cm-1. HR-MS (FAB+) m/z: 882.2389 (Calcd for
C34H54INO16Na: 882.2385).
15-(p-Iodophenyl)pentadecyl
2-acetamido-2-deoxy--D-glucopyranosyl-(1
→
2)--D-manno-
pyranosyl-(1→6)--D-glucopyranoside (1c)
Sodium methoxide (28% in MeOH, 20 L) was added to a solution of 10c (28.9 mg, 21.6 mol) in
MeOH (2 mL), which was stirred for 30 min at room temperature. The reaction mixture was treated in the

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HETEROCYCLES, Vol. 83, No. 12, 2011
same manner as the synthesis of 1a. The residue was purified by a recycle HPLC on a reversed phase
1
column (MeOH: H2O = 9:1) to afford 1c (15.0 mg, 73%). []D o (c 0.62, MeOH). H-NMR
(C5D5N+D2O)  1.23 (20H, m), 1.33-1.36 (2H, m), 1.50-1.53 (2H, m), 1.60-1.68 (2H, m), 2.18 (3H, s),
2.47 (2H, t, J = 7.9 Hz), 3.65 (1H, dt, J = 6.6, 9.5 Hz), 3.88 (1H, ddd, J = 2.4, 4.9, 9.5 Hz), 3.96-4.02 (2H,
m), 4.08-4.23 (5H, m), 4.26-4.30 (2H, m), 4.35-4.56 (8H, m), 4.64 (1H, t, J = 9.5 Hz), 4.79 (1H, d, J = 7.9
Hz, Glc-1), 5.20 (1H, d, J = 6.4 Hz, GlcN-1), 5.52 (1H, br s), 6.98 (2H, br d, J = 8.2 Hz), 7.70 (2H, br d, J
13
= 8.2 Hz). C-NMR (C5D5N+D2O) : 23.8, 26.5, 29.4, 29.7, 29.86 (2C), 29.93 (3C), 30.0 (3C), 30.3,
31.5, 35.5, 57.9, 62.3, 62.9, 67.4, 68.8, 69.9, 71.4, 71.8, 72.1, 75.1, 75.3, 75.7, 76.3, 78.6 (2C), 80.0, 91.4,
98.9 (Man-1), 102.5 (GlcN-1), 104.7 (Glc-1), 131.1 (2C), 137.6 (2C), 142.9, 171.5. IR (KBr) : 3429,
2924, 2853, 1636, 1067 cm-1. HR-MS (FAB+) m/z: 980.3484 (Calcd for C41H68INO16Na: 980.3481).
2-(p-Tributylstannylphenyl)ethyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1→2)-
3,4,6-tri-O-acetyl--D-mannopyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (19a)
Potassium acetate (7.6 mg, 77.4 mol), [1,1’-bis(diphenylphoshino)ferrocene]dichloropalladium(II)
complex with CH2Cl2 (1:1) (2.8 mg, 3.4 mol), and bis(tributyltin) (27 L, 53.4 mol) were added to a
solution of 10a (30.2 mg, 26.2 mol) in NMP (1 mL). After stirring the reaction mixture for 2 h at room
temperature, the mixture was extracted with EtOAc, washed with distilled water and a saturated aqueous
solution of sodium chloride, successively, dried over sodium sulfate, and condensed in vacuo. The residue
was purified by amine modified silica gel column chromatography (hexane : EtOAc = 1:2) to afford 19a
1
(21.2 mg, 61%). []D 21.0o (c 0.58, CHCl3). H-NMR (C5D5N)  0.87 (9H, t, J = 7.3 Hz), 1.09-1.13
(6H, m), 1.34 (6H, sextet, J = 7.3 Hz), 1.56-1.63 (6H, m), 1.97, 1.975, 1.980, 1.983, 2.01, 2.080, 2.083,
and 2.10 (each 3H, s), 2.11 (6H, s), 3.00 (1H, dt, J = 6.5, 13.9 Hz), 3.06 (1H, dt, J = 7.2, 13.9 Hz),
3.74-3.79 (1H, m, Glc-6), 3.88 (1H, dt, J = 7.5, 9.7 Hz, -OCH2), 4.03-4.14 (4H, m, GlcN-2, GlcN-5,
Glc-5, Glc-6), 4.29 (1H, dd, J = 2.0, 12.2 Hz, GlcN-6), 4.35-4.41 (2H, m, Man-5, -OCH2), 4.45 (1H, dd, J
= 2.4, 12.1 Hz, Man-6), 4.52 (1H, dd, J = 5.2, 12.1 Hz, Man-6), 4.63 (1H, dd, J = 5.7, 12.2 Hz, GlcN-6),
4.81 (1H, dd, J = 1.3, 3.5 Hz, Man-2), 4.92 (1H, d, J = 8.1 Hz, Glc-1), 5.29 (1H, d, J =1.3 Hz, Man-1),
5.42 (1H, t, J = 10.1 Hz, GlcN-4), 5.44 (1H, dd, J = 8.1, 9.7 Hz, Glc-2), 5.45 (1H, br t, J = 10.8 Hz,
Glc-4), 5.57 (1H, d, J = 8.4 Hz, GlcN-1), 5.63 (1H, dd, J = 3.5, 10.3 Hz, Man-3), 5.73 (1H, t, J = 9.7 Hz,
Glc-3), 5.88 (1H, t, J = 10.3 Hz, Man-4), 6.08 (1H, dd, J = 9.3, 10.6 Hz, GlcN-3), 7.40 (2H, br d, J = 7.9
Hz), 7.60 (2H, br d, J = 7.9 Hz), 9.27 (1H, d, J = 8.2 Hz). 13C-NMR (C5D5N) : 9.7 (3C), 13.8 (3C), 20.5
(3C), 20.7 (6C), 23.2, 27.6 (3C), 29.4 (3C), 36.3, 55.7 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.4
(Man-4), 67.1 (Glc-6), 69.6 (Glc-4), 69.9 (GlcN-4), 70.0 (Man-5), 71.0 (-OCH2, Man-3), 71.9 (Glc-2),
72.2 (GlcN-5), 72.6 (GlcN-3), 73.0 (Glc-5), 73.5 (Glc-3), 74.4 (Man-2), 98.3 (Man-1), 99.7 (GlcN-1),

HETEROCYCLES, Vol. 83, No. 12, 2011
2799
101.1 (Glc-1), 129.4 (2C), 137.0 (2C), 139.1, 139.2, 169.5, 169.88, 169.93, 170.0, 170.4, 170.48, 170.53,
170.6, 170.7, 171.0. IR (CHCl3) : 3020, 2928, 1753, 1682, 1514, 1464, 1429, 1367, 1251, 1138, 1069,
1040 cm-1. HR-MS (FAB+) m/z: 1340.4495 (Calcd for C58H87NO25SnNa: 1340.4487).
8-(p-Tributylstannylphenyl)octyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-(1→2)-
3,4,6-tri-O-acetyl--D-mannopyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (19b)
Potassium acetate (8.9 mg, 90.7 mol), [1,1’-bis(diphenylphoshino)ferrocene]dichloropalladium(II)
complex with CH2Cl2 (1:1) (2.5 mg, 3.1 mol), and bis(tributyltin) (30 L, 59.4 mol) were added to a
solution of 10b (37.2 mg, 30.1 mol) in NMP (1 mL). After stirring the reaction mixture for 2 h at room
temperature, the mixture was extracted with EtOAc, washed with distilled water and a saturated aqueous
solution of sodium chloride, successively, dried over sodium sulfate, and condensed in vacuo. The residue
was purified by amine modified silica gel column chromatography (hexane : EtOAc = 1:1) to afford 19b
(12.9 mg, 31%). []D o (c 0.80, CHCl3). 1H-NMR (C5D5N)  0.87 (9H, t, J = 7.3 Hz), 1.11-1.15 (6H,
m), 1.16-1.39 (8H, m), 1.35 (6H, sextet, J = 7.3 Hz), 1.51-1.71 (10H, m), 1.97, 1.99, 2.02, and 2.07 (each
3H, s), 2.09 (9H, s), 2.099, 2.103, and 2.11 (each 3H, s), 2.60 (2H, t, J = 7.9 Hz), 3.62 (1H, dt, J = 7.0, 9.5
Hz, -OCH2), 3.76-3.79 (1H, m, Glc-6), 4.01 (1H, ddd, J = 2.2, 5.5, 10.1 Hz, GlcN-5), 4.04-4.16 (4H, m,
GlcN-2, Glc-5, Glc-6, -OCH2), 4.28 (1H, dd, J = 2.2, 12.3 Hz, GlcN-6), 4.38 (1H, ddd, J = 2.4, 5.1, 9.9
Hz, Man-5), 4.45 (1H, dd, J = 2.4, 12.1 Hz, Man-6), 4.53 (1H, dd, J = 5.1, 12.1 Hz, Man-6), 4.62 (1H, dd,
J = 5.5, 12.3 Hz, GlcN-6), 4.79 (1H, dd, J = 1.5, 3.5 Hz, Man-2), 4.92 (1H, d, J = 8.1 Hz, Glc-1), 5.28
(1H, d, J = 1.5 Hz, Man-1), 5.41 (1H, t, J = 9.3 Hz, GlcN-4), 5.45 (1H, dd, J = 8.1, 9.7 Hz, Glc-2), 5.46
(1H, t, J = 9.5 Hz, Glc-4), 5.54 (1H, d, J = 8.4 Hz, GlcN-1), 5.61 (1H, dd, J = 3.5, 10.1 Hz, Man-3), 5.77
(1H, t, J = 9.7 Hz, Glc-3), 5.90 (1H, t, J = 10.1 Hz, Man-4), 6.04 (1H, dd, J = 9.3, 10.6 Hz, GlcN-3), 7.36
13
(1H, br d, J = 7.9 Hz), 7.63 (1H, br d, J = 7.9 Hz), 9.26 (1H, d, J = 8.1 Hz). C-NMR (C5D5N) : 9.8
(3C), 13.9 (3C), 20.47, 20.49, 20.52, 20.7 (5C), 20.8, 23.2, 26.2, 27.6 (3C), 29.4 (3C), 29.55, 29.57, 29.78,
29.83, 31.9, 36.2, 55.7 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.5 (Man-4), 67.2 (Glc-6), 69.6 (Man-5),
69.8 (GlcN-4), 70.1 (Glc-4), 70.3 (-OCH2), 71.0 (Man-3), 72.16 (Glc-2), 72.21 (GlcN-5), 72.6 (GlcN-3),
72.9 (Glc-5), 73.6 (Glc-3), 74.5 (Man-2), 98.3 (Man-1), 99.7 (GlcN-1), 101.1 (Glc-1), 128.9 (2C), 137.0
(2C), 138.4, 143.1, 169.6, 169.87, 169.94, 170.0, 170.4, 170.48, 170.54, 170.6, 170.7, 171.0. IR (CHCl3)
: 3030, 2930, 2855, 1751, 1682, 1514, 1464, 1431, 1367, 1252, 1040 cm-1. HR-MS (FAB+) m/z:
1424.5430 (Calcd for C64H99NO25SnNa: 1424.5426).
15-(p-Tributylstannylphenyl)pentadecyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-glucopyranosyl-
(1→2)-3,4,6-tri-O-acetyl--D-manno- pyranosyl-(1→6)-2,3,4-tri-O-acetyl--D-glucopyranoside (19c)

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HETEROCYCLES, Vol. 83, No. 12, 2011
Tetrakis(triphenylphosphine)palladium(0) (10.1 mg, 8.7 mol), triphenylphosphine (2.3 mg, 8.8 mol),
and bis(tributyltin) (74 L, 146.5 mol) were added to a solution of 10c (113.1 mg, 91.4 mol) in toluene
(2 mL). After stirring the reaction mixture for 5 h at 85 ºC, the mixture was condensed in vacuo. The
residue was purified by amine modified silica gel column chromatography (hexane: EtOAc = 1:1) to
1
afford 19c (7.7 mg, 16%). []D 4.2o (c 1.36, CHCl3). H-NMR (C5D5N)  0.87 (9H, t, J = 7.3 Hz),
1.11-1.15 (6H, m), 1.21-1.40 (30H, m), 1.54-1.70 (8H, m), 1.97, 1.99, 2.02, 2.07, 2.09, and 2.097 (each
3H, s), 2.101 (6H, s), 2.11 (6H, s), 2.62 (2H, t, J = 7.9 Hz), 3.64 (1H, dt, J = 6.8, 9.7 Hz, -OCH2),
3.76-3.78 (1H, m, Glc-6), 4.01 (1H, ddd, J = 2.2, 5.5, 10.1 Hz, GlcN-5), 4.05-4.16 (4H, m, GlcN-2, Glc-5,
Glc-6, -OCH2), 4.28 (1H, dd, J = 2.2, 12.1 Hz, GlcN-6), 4.39 (1H, ddd, J = 2.4, 5.1, 10.3 Hz, Man-5),
4.45 (1H, dd, J = 2.4, 12.1 Hz, Man-6), 4.54 (1H, dd, J = 5.1, 12.1 Hz, Man-6), 4.62 (1H, dd, J = 5.5,
12.1 Hz, GlcN-6), 4.80 (1H, dd, J = 1.7, 3.5 Hz, Man-2), 4.93 (1H, d, J = 8.1 Hz, Glc-1), 5.28 (1H, d, J =
1.7 Hz, Man-1), 5.42 (1H, t, J = 9.3 Hz, GlcN-4), 5.45 (1H, dd, J = 8.1, 9.7 Hz, Glc-2), 5.46 (1H, t, J =
9.7 Hz, Glc-4), 5.54 (1H, d, J = 8.6 Hz, GlcN-1), 5.62 (1H, dd, J = 3.5, 10.3 Hz, Man-3), 5.77 (1H, t, J =
9.5 Hz, Glc-3), 5.90 (1H, t, J = 10.3 Hz, Man-4), 6.05 (1H, dd, J = 9.3, 10.6 Hz, GlcN-3), 7.38 (2H, br d,
13
J = 7.9 Hz), 7.64 (2H, br d, J = 7.9 Hz), 9.26 (1H, d, J = 8.1 Hz). C-NMR (C5D5N) : 9.8 (3C), 13.9
(3C), 20.47, 20.50, 20.52, 20.6 (2C), 20.7 (3C), 20.8, 23.2, 26.3, 27.6 (3C), 29.4 (3C), 29.5, 29.6, 29.7,
29.8, 29.88, 29.92, 29.98 (2C), 30.0 (3C), 31.9, 36.2, 55.7 (GlcN-2), 62.7 (GlcN-6), 63.0 (Man-6), 66.5
(Man-4), 67.2 (Glc-6), 69.6 (Man-5), 69.8 (GlcN-4), 70.1 (Glc-4), 70.3 (-OCH2), 71.0 (Man-3), 72.17
(Glc-2), 72.22 (GlcN-5), 72.6 (GlcN-3), 72.9 (Glc-5), 73.6 (Glc-3), 74.5 (Man-2), 98.3 (Man-1), 99.7
(GlcN-1), 101.1 (Glc-1), 128.9 (2C), 137.0 (2C), 138.4, 143.2, 169.6, 169.9, 169.95, 169.97, 170.4,
170.48, 170.54, 170.6, 170.7, 171.0. IR (CHCl3) : 3042, 2928, 2855, 1751, 1682, 1603, 1518, 1464,
1431, 1367, 1256, 1040 cm-1. HR-MS (FAB+) m/z: 1522.6519 (Calcd for C71H113NO25SnNa: 1522.6521).
Radioiodinated 1a ([125I]1a)
5% H2O2 aq. (10 L), 0.1 M HCl aq. (10 L), and [125I]NaI (576 Ci) were added to a solution of
tributyltin derivative 19a (100 g) in MeCN (20 L). After stirring the reaction mixture at room
temperature for 30 min, the mixture was added to a saturated aqueous solution of sodium thiosulfate,
which was extracted with EtOAc and condensed in vacuo. The residue was treated with MeOH (20 L)
and sodium methoxide (28% in MeOH, 3 L) for 30 min. The mixture was neutralized with 1 M
hydrochloric acid. Purification of the residue on HPLC equipped with a Cosmosil 5C18 AR-300 column
(4.6 × 150 mm, MeCN: H2O = 20 :80) with a flow rate of 1.0 mL/min afforded [125I]1a (408 Ci), and its
identity was identified by co-injection with 1a. The radiochemical yield was 71% and the radiochemical
purity was >99%.

HETEROCYCLES, Vol. 83, No. 12, 2011
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Radioiodinated 1b ([125I]1b)
5% H2O2 aq. (10 L), 0.1 M HCl aq. (10 L), and [125I]NaI (400 Ci) were added to a solution of
tributyltin derivative 19b (100 g) in MeCN (20 L). After stirring the reaction mixture at room
temperature for 30 min, the mixture was added to a saturated aqueous solution of sodium thiosulafte,
which was extracted with EtOAc and condensed in vacuo. The residue was treated with MeOH (20 L)
and sodium methoxide (28% in MeOH, 3 L) for 30 min. The mixture was neutralized with 1 M
hydrochloric acid. Purification of the residue on HPLC equipped with a Cosmosil 5C18 AR-300 column
(4.6 × 150 mm, MeCN :H2O = 40 :60) with a flow rate of 1.0 mL/min afforded [125I]1b (304 Ci), and its
identity was identified by co-injection with 1b. The radiochemical yield was 76% and the radiochemical
purity was >99%.
Radioiodinated 1c ([125I]1c)
5% H2O2 aq. (10 L), 0.1 M HCl aq. (10 L), and [125I]NaI (600 Ci) were added to a solution of
tributyltin derivative 19c (100 g) in MeCN (20 L). After stirring the reaction mixture at room
temperature for 30 min, the mixture was added to a saturated aqueous solution of sodium thiosulafte,
which was extracted with EtOAc and condensed in vacuo. The residue was treated with MeOH (20 L)
and sodium methoxide (28% in MeOH, 3 L) for 30 min. The mixture was neutralized with 1 M
hydrochloric acid. Purification of the residue on HPLC equipped with a Cosmosil 5C18 AR-300 column
(4.6 × 150 mm, MeCN :H2O = 60 :40) with a flow rate of 1.0 mL/min afforded [125I]1c (326 Ci), and its
identity was identified by co-injection with 1c. The radiochemical yield was 54% and the radiochemical
purity was >99%.
REFERENCES AND NOTE
1. R. D. Cummings, I. S. Trowbridge, and S. Kornfeld, J. Biol. Chem., 1982, 257, 13421.
2. K. Yamashita, Y. Tachibana, T. Ohkura, and A. Kobata, J. Biol. Chem., 1985, 260, 3963.
3. M. Pierce and J. Arango, J. Biol. Chem., 1986, 261, 10772.
4. J. W. Dennis, S. Laferte, C. Waghorne, M. L. Breitman, and R. S. Kerbel, Science, 1987, 236, 582.
5. J. W. Dennis and S. Laferte, Cancer Res., 1989, 49, 945.
6. B. Fernandes, U. Sagman, M. Auger, M. Demetrio, and J. W. Dennis, Cancer Res., 1991, 51, 718.
7. E. Miyoshi, A. Nishikawa, Y. Ihara, J. Gu, T. Sugiyama, N. Hayashi, H. Fusamoto, T. Kamada, and
N. Taniguchi, Cancer Res., 1993, 53, 3899.
8. K. Murata, E. Miyoshi, M. Kameyama, O. Ishikawa, T. Kabuto, Y. Sasaki, M. Hiratsuka, H.
Ohigashi, S. Ishiguro, S. Ito, H. Honda, F. Takemura, N. Taniguchi, and S. Imaoka, Clin. Cancer

2802
HETEROCYCLES, Vol. 83, No. 12, 2011
Res., 2000, 6, 1772.
9. J. W. Dennis, J. Pawling, P. Cheung, E. Partridge, and M. Demetriou, Biochim. Biophys. Acta, 2002,
157, 414.
10. T. Saito, E. Miyoshi, K. Sasai, N. Nakano, H. Eguchi, K. Honke, and N. Taniguchi, J. Biol. Chem.,
2002, 277, 17002.
11. T. Mukai, M. Hagimori, K. Arimitsu, T. Katoh, M. Ukon, T. Kajimoto, H. Kimura, Y. Magata, E.
Miyoshi, N. Taniguchi, M. Node, and H. Saji, Bioorg. Med. Chem., 2011, 19, 4312.
12. T. Kajimoto, Y. Ishioka, T. Katoh, and M. Node, Bioorg. Med. Chem. Lett., 2006, 16, 5736.
13. T. Kajimoto, Y. Ishioka, T. Katoh, and M. Node, J. Carbohydr. Chem., 2007, 26, 469.
14. T. Kajimoto, K. Arimitsu, M. Ozeki, and M. Node, Chem. Pharm. Bull., 2010, 58, 758.
15. Hydrogenolysis of 14 or 15 with Pd/C or Pd(OH)2/C did not proceed.
16. T. L. Ho and G. A. Olah, Angew. Chem., Int. Ed. Engl., 1976, 15, 774, See also, M. E. Jung and M.
A. Lyster, J. Am. Chem. Soc., 1977, 99, 968.
17. A. N. Pinchuk, M. A. Rampy, M. A. Longino, R. W. Scott Skinner, M. D. Gross, J. P. Weichert, and
R. E. Counsell, J. Med. Chem., 2006, 49, 2155.
18. Y. Hayakawa, H. Kato, M. Uchiyama, H. Kajino, and R. Noyori, J. Org. Chem., 1986, 51, 2400.
19. A. Hasegawa, T. Nagahama, H. Ohki, K. Hotta, H. Ishida, and M. Kiso, J. Carbohydr. Chem., 1991,
10, 493.
20. M. E. Mahoney, A. Oliver, O. Einarsdottir, and J. P. Konopelski, J. Org. Chem., 2009, 74, 8212.
21. W. Qu, K. Ploessl, H. Truong, M-P. Kung, and H. K. Kung, Bioorg. Med. Chem. Lett., 2009, 19,
3382.