The application of phenylmethanethiol and benzenethiol derivatives as odorless organosulfur reagents in the synthesis of thiosugars and thioglycosides

Article abstract of DOI:10.1016/j.carres.2005.07.011

p-Octyloxyphenylmethanethiol and p-dodecylbenzenethiol were prepared as new odorless organosulfur reagents. Thiosugars and thioglycosides were synthesized using these reagents without encountering any malodorous procedures.

Full text of DOI:10.1016/j.carres.2005.07.011

Carbohydrate
RESEARCH
Carbohydrate Research 340 (2005) 2360–2368
The application of phenylmethanethiol and benzenethiol
derivatives as odorless organosulfur reagents in the synthesis of
thiosugars and thioglycosides
Jun-ya Hasegawa, Masahiro Hamada, Tetsuo Miyamoto, Kiyoharu Nishide,
Tetsuya Kajimoto, Jun-ichi Uenishi and Manabu Node*
Departments of Pharmaceutical Manufacturing Chemistry and Pharmaceutical Organic Chemistry, 21st Century COE program,
Kyoto Pharmaceutical University, 1 Shichono-cho, Misasagi, Yamashina-ku, Kyoto 607-8414, Japan
Received 29 March 2005; accepted 12 July 2005
Available online 6 September 2005
Abstract—p-Octyloxyphenylmethanethiol and p-dodecylbenzenethiol were prepared as new odorless organosulfur reagents. Thio-
sugars and thioglycosides were synthesized using these reagents without encountering any malodorous procedures.
Ó 2005 Elsevier Ltd. All rights reserved.
Keywords: Odorless organosulfur reagents; Thiosugars; Thioglycosides; p-Octyloxyphenylmethanethiol; p-Dodesylbenzenethiol
1. Introduction
and in the reductive workup procedure of ozonolysis
and other sulfur-related reactions, except for the intro-
duction of sulfur groups (BnS, PhS, HS).4a–g In addi-
tion, we found that the complexes of borane with the
odorless sulfides were no less useful reagents than is
the boraneÆdimethyl sulfide complex in the hydrobora-
tion and reduction of carbonyl groups.4h Therefore, we
next tried to develop new odorless organosulfur reagents
that are suitable for the preparation of thiosugars and
thioglycosides as a part of our study on odorless organic
synthesis.
Thiosugars, in which the ring oxygen of the monosac-
charide is replaced with a sulfur atom, have been utilized
in the synthesis of bioactive oligosaccharides as excellent
analogs of monosaccharides because of their tolerant
reactivity with glycosidases.1 Naturally occurring thio-
sugar derivatives, as well as synthesized derivatives,
show inhibitory activity against glycosidases, for exam-
ple, salacinol isolated from Salacia reticulata is a potent
inhibitor of a-glucosidases.2 On the other hand, thiogly-
cosides in which the anomeric carbon is linked to a
sulfur atom have been often prepared as valid glycosyl
donors for use in glycosidation reactions.3 However, in
the preparation of both thiosugars and thioglycosides,
malodorous reagents such as phenylmethanethiol and
benzenethiol have been unavoidably employed as the
reagents for the source of sulfur.
2. Results and discussion
Initially, we tried to modify the structure of odorless
p-heptylphenylmethanethiol (4), but the approach was
dropped because of the unsatisfactory overall yield
when the reagent was prepared from dibromoxylene.4a
Since thiols and sulfides having more than 14 tandem-
linked carbons do not smell at all due to the increase
in molecular weight,4a p-hexyloxyphenylmethanethiol
(5) was designed as a new type of odorless thiol by the
replacement of one methylene of 4 with an oxygen atom.
Recently, we have devised odorless thiols and methyl
sulfides that are useful in the Corey–Kim oxidation, in
the demethylation of methyl ethers or methyl esters,
*
Corresponding author. Tel.: +81 75 595 4639; fax: +81 75 595
4775; e-mail: node@mb.kyoto-phu.ac.jp
0008-6215/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2005.07.011

J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
2361
SH
C7H15
4
1) C6H13Br , K2CO3
2) NaBH4
1) MsCl, Et3N,CH2Cl2
2) thiourea, EtOH
OH
OH
CHO
SH
SH
88%
C6H13
O
3)10 %-NaOH
C6H13
O
2
3
5
4) LiAlH4
41%
OH
1) C8H17Br , K2CO3
2) NaBH4
1) thiourea, p-TsOH
MeCN
1
76%
2 )10%NaOH
77%
C8H17O
C8H17O
6
Scheme 1.
O-Alkylation of p-hydroxybenzaldehyde (1) with
bromohexane in the presence of potassium carbonate,
followed by reduction with sodium borohydride, gave
p-hexyloxybenzyl alcohol (2), which was converted to
5 in satisfactory yield by the sequence of mesylation,
substitution with thiourea, alkaline hydrolysis, and
reduction with lithium aluminum hydride. Unfortu-
nately 5 was still slightly malodorous. Accordingly, p-
octyloxyphenylmethanethiol (6), which has two more
methylenes than 5, was synthesized as a new odorless
phenylmethanethiol derivative on the basis of our expe-
rience of odor tests.4a The synthetic route of 6 was quite
similar to that of 5, that is, 1 was treated with bromo-
octane, followed by reduction with sodium borohydride,
to give p-octyloxybenzyl alcohol (3), which was
converted to 6 via the thionium salt in good yield. As
expected, 6 was odorless due to its lower volatility
(Scheme 1).4a
On the other hand, alkylbenzenethiol and its analogs
(10a–c) that have different methylene lengths can be pre-
pared from p-alkylphenols (7a–c) by taking advantage
of the Newman–Kwart rearrangement, the O!S rear-
rangement from 8a–c to 9a–c, in excellent yields
(Scheme 2).4b,5 As expected, the alkylbenzenethiols with
longer alkyl chains became less malodorous (Table 1).
In spite of containing a small amount of analogs hav-
ing more or less methylenes, dodecylbenzenethiol (10d)6
having five more methylenes in length than 10b was
easily prepared by reduction with lithium aluminum
hydride from 4-dodecylbenzenesulfonic acid (11), which
is available as an inexpensive material used in synthetic
detergents.ꢀ In addition, reduction of dodecylbenzene-
sufonyl chloride (12)ꢁ yielded a better result (see Scheme
3).
Having succeeded in the synthesis of odorless benzyl-
methanethiol (6) and benzenethiol (10b, 10d), we applied
these reagents to the synthesis of thiosugars and
thioglycosides.
Methyl 3,5-di-O-benzyl-2-deoxy-D-erythro-pentofur-
anoside (13) was treated with 6 to afford the bis(4-octyl-
oxy)benzyl dithioacetal 14a.7 The hydroxyl group was
mesylated, and the following intramolecular attack of
a sulfur atom to the mesylated carbon in the presence
of sodium iodide and barium carbonate gave 4-octyl-
oxybenzyl 3,5-di-O-benzyl-2-deoxy-1,4-dithio-L-threo-
pentofuranoside (15a). It is noteworthy that the combi-
nation of bis(4-octyloxy)benzyl dithioacetal 14a and
DMF provided a much better result in this reaction than
that of the bisbenzyl dithioacetal 14b and acetone to af-
ford 15b.7 In order to prepare 3,5-di-O-benzyl-2-deoxy-
5-thio-D-erythro-pento-furanoside, the configuration of
the hydroxyl group at C-4 should be inverted in advance
of nucleophilic substitution on the mesylated carbon.
Therefore, the configuration of the secondary alcohol
of 14a was first inverted to afford 16a by the Mitsunobu
reaction with triphenylphosphine, benzoic acid, and
DIAD, and following alkaline hydrolysis, gave 16b.
Mesylation of the hydroxyl group of 16b and successive
treatment with sodium iodide and barium carbonate
gave 4-octyloxybenzyl 3,5-di-O-benzyl-2-deoxy-1,4-
dithio-D-erythro-pentofuranoside (17) (Scheme 4). The
overall yield from 13 to 17 was six times higher than that
reported in the literature.7
Thioglycosides (19a–c) were next prepared using
dodecanethiol (10e), 10b, and 10d as valid glycosyl do-
nors for glycosidation. Per-O-acetylated D-glucopyrano-
side (18) was treated with 10e, 10b, and 10d, respectively,
in the presence of BF3ÆEt2O to afford 19a–c. Here, the
thioglycoside (19c) thus obtained was used as the glyco-
syl donor without purification. Glycosylation of methyl
2,3,4-tri-O-acetyl-a-D-glucopyranoside (20) with 19a–c
in the presence of N-iodosuccinimide (NIS) and BF3Æ
Et2O gave methyl 2,3,4,6-tetra-O-acetyl-D-glucopyran-
osyl-(1!6)-2,3,4-tri-O-acetyl-a-D-glucopyranoside (21)
ꢀ Because 11 was purchased as an industrial-grade material, it included
analogs with more or less methylenes as contaminants within ca. 5%.
ꢁ Compound 12 was purchased from Wako Pure Chemical Industries,
Ltd., Japan.

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J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
S
O
OH
SH
O
NMe2
S
NMe2
Me2CC(S)Cl
NaH
1) LiAlH4
2) HCl
∆
85 o
C
R
R
R
R
7
8
9
10
295 oC
260 oC
300 oC
96%
80%
88%
a: R = C6H13
b: R = C7H15
c: R = C8H17
100%
100%
93%
81%
74%
84%
Scheme 2.
Table 1. The odor scale of benzenethiols
glycosides to glycosidation proceeded without the gener-
ation of a stench (Scheme 5).
Entry
Thiols
Carbon
length
Odor scale
A
5
B
5
4
1
3. Experimental
3.1. General
2
3
6
2
0
1
2
Infrared (IR) spectra were recorded on a JASCO IR-810
or a Shimadzu FTIR-8300 diffraction grating infrared
spectrophotometer. 1H NMR spectra were obtained
on a JEOL JNM-AL300, a Varian XL-300, or a Varian
Unity INOVA-400 spectrometer with tetramethylsilane
as the internal standard. 13C NMR spectra were ob-
tained on a Varian Unity INOVA-400 spectrometer
with CDCl3 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 auto-
matic digital polarimeter. Wako Gel C-200 (silica gel)
(100–200 mesh, Wako) was used for open column chro-
matography. Flash column chromatography was per-
formed by using Silica Gel 60N (Kanto Chemical Co.,
Inc.) as a solid support for the immobile phase. Kieselgel
60 F-254 plates (E. Merck) were used for thin-layer
chromatography (TLC). Unless purification with silica
gel gave a compound that was deemed pure enough,
the compounds were further treated with a recycle-mode
HPLC (JAI LC-908) on a GPC column (JAIGEL 1H
and 2H). In this case diastereomeric mixtures were also
separated by a recycle-mode HPLC (JAI LC-908) on a
silica gel column (Kusano Si-10) after the purification
mentioned above.
10
4
11
1
0
5
6
12
16
1
0
1
0
SH
SO3H
SO2Cl
Ph3P, I2
92%
C12H25
C12H25
10d
11
LiAlH4
97%
10d
C12H25
12
Scheme 3.
in better yields than the reaction with 19d prepared from
benzenethiol and 18 under malodolous conditions.8 In
addition, the glycosylation with alkylphenyl 2,3,4,6-tet-
ra-O-acetyl-1-thio-D-glucopyranoside (19b, 19c) gave
only the b-(1!6)-linked glycoside of 21 as same as the
reaction with 19d, while the reaction with dodecyl
2,3,4,6-tetra-O-acetyl-1-thio-glycopyranoside (19a) gave
a mixture of a and b anomers of 21. Finally, it is note-
worthy that all the steps from the preparation of thio-
3.2. p-Octyloxyphenylmethanol (3)
A mixture of p-hydroxybenzaldehyde (1, 15.0 g) and
K2CO3 (33.9 g) in DMF (100 mL) was heated at 90 °C
for 1 h, and chilled to room temperature. After adding
bromooctane (25.4 mL), the mixture was stirred for
3 h and filtered. The filtrate was condensed in vacuo,
diluted with MeOH (100 mL), and treated with NaBH4

J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
2363
1) MsCl, Pyr.
2) NaI, BaCO3
in DMF
14a
6 or
PhCH2SH
BnO
OBn SR
SR
S
O
SR
OMe
BnO
BnO
HCl
OBn
14b
OBn
13
1) MsCl, Pyr.
2) NaI, BaCO3
in acetone
OH
15a: R = 4-octyloxybenzyl (73%)
15b: R = benzyl (40%)
14a: R = 4-octyloxybenzyl (84%)
14b: R = benzyl (85%)
BnO
S
OBn SR
1) BzOH, PPh3
DIAD
1) MsCl, Pyr.
SR
BnO
SR
14a
2) NaI, BaCO3
DMF
2) NaOMe
78%
OBn
OR'
16a: R = 4-octyloxybenzyl, R' = Bz
16b: R = 4-octyloxybenzyl, R' = H
17
98%
Scheme 4.
HO
O
OAc
RSH
AcO
AcO
AcO
AcO
AcO
OMe
O
20
OAc
.
SR
O
O
O
.
O
BF3 OEt2
OAc
OAc
OAc
OAc
OAc
.
NIS, BF3 OEt2
in CH2Cl2
AcO
OAc
AcO
AcO
OMe
OAc
OAc
18
OAc
19
21
a: 87% (β:α = 2:1)
b: 81% (β:α = 1:0)
c: 87% (β:α = 1:0) (2 steps)
a: R = dodecyl (99%)
b: R = 4-heptylphenyl (99%)
c: R = 4-dodecylphenyl
d: R = phenyl (99%)
d: 72% (β:α = 1:0)
Scheme 5.
(13.9 g) for 1.5 h. After the reaction, MeOH was evapo-
rated and partitioned between Et2O and water. The or-
ganic layer was successively washed with molar HCl and
brine, dried over MgSO4, and evaporated. Crystalliza-
tion of the residue from n-hexane and further purifica-
tion of its mother liquor by silica gel column
urea (80 mg, 1.1 mmol) in acetonitrile (25 mL), and the
reaction mixture was refluxed for 1 h. After adding
10% aq NaOH, the mixture was refluxed for another
4 h, and the reaction solution was acidified with 2.5 M
HCl until the pH value reached pH 1. The reaction mix-
ture was extracted with Et2O, and the organic layer was
washed with brine, dried over MgSO4, and evaporated.
The residue was purified by silica gel column chroma-
tography (5:1 hexane–benzene) to afford 6 (208 mg,
77%). IR (CHCl3): 3021–2856, 2580, 1610–1583, 1512–
chromatography (5:1 hexane–AcOEt) afforded
3
(27.2 g, 94%) as colorless plates: mp 45.5–46.5 °C; IR:
3606, 3446, 3022–2871, 2360, 1612–1583, 1512–
1
1469 cmÀ1; H NMR (400 MHz, CDCl3): d 7.30–7.27
1
(m, arom 2H), 6.89 (dt, J 8.7, 2.5 Hz, arom 2H), 4.61
(s, 2H), 3.95 (t, J 6.5 Hz, 2H), 1.77 (quintet, J 5.6 Hz,
2H), 1.54 (s, 1H), 1.45 (quintet, J 7.1 Hz, 2H), 1.39–
1.28 (m, 8H), 0.89 (br t, J 6.9 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d 158.8, 132, 128.6 (2C), 114.6
(2C), 68, 65, 31, 29.3, 29.25, 29.23, 26, 22.6, 14.1; MS:
m/z 236 (M+, 23.8), 124 (100), 106 (57); HRMS: Calcd
for C15H24O2, m/z 236.1776; found, m/z 236.1780. Anal.
Calcd for C15H24O2: C, 76.04; H, 10.26. Found: C,
76.23; H, 10.24.
1434 cmÀ1; H NMR (400 MHz, CDCl3): d 7.22 (dt, J
8.79 and 2.51 Hz, arom 2H), 6.83 (dt, J 8.8 and
2.6 Hz, arom 2H), 3.93 (t, J 6.6 Hz, 2H), 3.71 (d, J
7.3 Hz, 2H), 1.76 (quintet, J 7.3 Hz, 1H), 1.73 (t, J
7.3 Hz, 1H), 1.51–1.27 (m, 10H), 0.89 (br t, J 7.0 Hz,
3H); 13C NMR (100 MHz, CDCl3): d 158.2, 133.0,
129.1 (2C), 114.6 (2C), 29.34, 29.30, 29.2, 28.4, 26.0,
22.6, 14.1. MS (20 eV): m/z 252 (M+, 5), 219 (69), 151
(8), 107 (100); HRMS: Calcd for C15H24OS, m/z
252.1548 (M+); found, m/z 252.1551.
3.3. p-Octyloxyphenylmethanethiol (6)
3.4. O-p-Hexylphenyl N,N-dimethylthiocarbamate (8a)
p-Octyloxyphenylmethanol (3) (250 mg, 1.06 mmol) and
p-TsOHÆH2O (190 mg) were added to a solution of thio-
A solution of p-hexylphenol (7a) (1.0 g, 5.6 mmol)
in DMF (5.0 mL) and N,N-dimethylthiocarbamoyl

2364
J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
chloride (832 mg, 6.73 mmol) was successively added to
a suspension of NaH (175 mg, 7.29 mmol) in DMF
(20 mL) at 0 °C, and the mixture was stirred at 85 °C
for 15 h. After the reaction was complete, 2% aq KOH
was added to the reaction mixture, which was then ex-
tracted with Et2O. The organic layer was washed with
water, dried over MgSO4, and evaporated. The residue
was purified by silica gel column chromatography (4:1
hexane–AcOEt) to afford 8a (1.5 g, 100%). IR (CHCl3):
3337, 2959, 2932, 2858, 1886, 1597, 1535, 1504, 1466,
3.7. O-p-Heptylphenyl N,N-dimethylthiocarbamate (8b)
IR (CHCl3): 3020, 2932, 2858, 1728, 1601, 1535, 1466,
1396, 1288, 1215, 1173, 1057, 1018, 837 cmÀ1 1H
;
NMR (300 MHz, CDCl3): d 7.17 (d, J 8.6 Hz, 2H),
6.95 (d, J 8.5 Hz, 2H), 3.45 (s, 3H), 3.33 (s, 3H), 2.60
(t, J 7.3 Hz, 2H), 1.53–1.63 (m, 2H), 1.23–1.36 (m,
8H), 0.87 (t, J 7.0 Hz, 3H); MS (70 eV): m/z 279 (M+,
22), 107 (8), 72 (100); HRMS: Calcd for C16H25NOS,
m/z 279.1657; found, m/z 279.1659.
1
1396, 1288, 1215 cmÀ1; H NMR (300 MHz, CDCl3):
d 7.18 (d, J 8.4 Hz, 2H), 6.96 (d, J 8.4 Hz, 2H), 3.45
(s, 3H), 3.32 (s, 3H), 2.60 (t, J 7.6 Hz, 2H), 1.56–1.66
(m, 2H), 1.23–1.38 (m, 6H), 0.88 (t, J 6.6 Hz, 3H); MS
(70 eV): m/z 265 (M+, 22), 249 (3), 161 (4), 91 (2), 88
(64), 72 (100); HRMS: Calcd for C15H23NOS, m/z
265.1500; found, m/z 265.1486.
3.8. S-p-Heptylphenyl N,N-dimethylthiocarbamate (9b)
IR (CHCl3): 3009, 2932, 2858, 1713, 1655, 1597, 1489,
1466, 1404, 1369, 1261, 1219, 1177, 1092, 1018, 910,
1
833 cmÀ1; H NMR (300 MHz, CDCl3): d 7.38 (d, J
8.4 Hz, 2H), 7.18 (d, J 8.4, 2H), 3.05 (br s, 6H), 2.60
(t, J 7.5 Hz, 2H), 1.57–1.65 (m, 2H), 1.25–1.35 (m,
8H), 0.87 (t, J 7.0 Hz, 3H); MS (70 eV): m/z 279 (M+,
7), 263 (2), 123 (3), 72 (100); HRMS: Calcd for
C16H25NOS, m/z 279.1657; found, m/z 279.1659.
3.5. S-p-Hexylphenyl N,N-dimethylthiocarbamate (9a)
O-p-Hexylphenyl N,N-dimethylthiocarbamate (8a)
(1.0 g, 3.8 mmol) was heated at 295 °C for 5.5 h, and
the residue was purified by silica gel column chromato-
graphy (4:1 hexane–AcOEt) to afford 9a (810 mg, 81%).
IR (CHCl3): 3009, 2932, 2858, 1713, 1663, 1597, 1489,
1466, 1404, 1369, 1261, 1204, 1177, 1092, 1018, 910,
3.9. p-Heptylbenzenethiol (10b)
IR (CHCl3): 2920, 2858, 1493, 1466, 1103 cmÀ1; MS
(70 eV): m/z 208 (M+, 28), 125 (5), 124 (10), 123 (100);
1H NMR (400 MHz, CDCl3): d 7.20 (d, J 8.1 Hz, 2H),
7.05 (d, J 8.1 Hz, 2H), 3.38 (s, 1H), 2.54 (t, J 7.6 Hz,
2H), 1.51–1.62 (m, 2H), 1.22–1.35 (m, 8H), 0.88 (t, J
6.8 Hz, 3H); HRMS: Calcd for C13H20S, m/z 294.1474;
found, m/z 294.1477.
833, 806 cmÀ1 1H NMR (300 MHz, CDCl3): d 7.38
;
(d, J 8.2 Hz, 2H), 7.18 (d, J 8.3 Hz, 2H), 3.05 (br s,
6H), 2.60 (t, J 7.6 Hz, 2H), 1.55–1.65 (m, 2H), 1.25–
1.39 (m, 6H), 0.87 (t, J 6.7, 3H); MS (70 eV): m/z 265
(M+, 17), 193 (1), 137 (1), 123 (3), 109 (2), 73 (4), 72
(100); HRMS: Calcd for C15H23NOS, m/z 206.1500;
found, m/z 265.1499.
3.10. O-p-Octylphenyl dimethylthiocarbamate (8c)
IR (CHCl3): 3020, 2932, 2858, 1597, 1535, 1504, 1466,
3.6. p-Hexylbenzenethiol (10a)
1396, 1288, 1242, 1196, 1173, 1142, 1018, 837 cmÀ1
;
1H NMR (300 MHz, CDCl3): d 7.18 (d, J 8.6 Hz, 2H),
6.95 (d, J 8.6 Hz, 2H), 3.45 (s, 3H), 3.33 (s, 3H), 2.60
(t, J 7.6 Hz, 2H), 1.54–1.66 (m, 2H), 1.22–1.35 (m,
10H), 0.87 (t, J 6.7 Hz, 3H); MS (70 eV): m/z 293
(M+, 5), 277 (2), 107 (15), 88 (35), 72 (100); HRMS:
Calcd for C17H27NOS, m/z 293.1813; found, m/z
293.1797.
Lithium aluminum hydride (200 mg, 0.76 mmol) was
added to
a solution of S-p-hexylphenyl N,N-di-
methylthiocarbamate (9a) (208 mg, 0.78 mmol) in Et2O
(2 mL) at 0 °C, and the reaction mixture was stirred at
65 °C for 3 h. After the reaction was completed, the
reaction was quenched with AcOEt and molar HCl,
and the mixture was extracted with Et2O. The organic
layer was washed with brine, dried over MgSO4, and
evaporated. The residue was purified by silica gel col-
umn chromatography (6:1 hexane–AcOEt) to afford
10a (122 mg, 96%). IR (CHCl3): 3032, 2959, 2341,
3.11. S-p-Octylphenyl dimethylthiocarbamate (9c)
IR (CHCl3): 3028, 3013, 2928, 2855, 1655, 1466, 1369,
1682, 1601, 1493, 1466, 1439, 1404, 1377, 1207 cmÀ1
;
1261, 1092, 1018, 910 cmÀ1 1H NMR (300 MHz,
;
1H NMR (400 MHz, CDCl3): d 7.20 (d, J 8.2 Hz, 2H),
7.05 (d, J 8.4 Hz, 2H), 3.39 (s, 1H), 2.54 (t, J 7.6, 2H),
1.53–1.61 (m, 2H), 1.21–1.34 (m, 6H), 0.88 (t, J
6.8 Hz, 3H); MS (70 eV): m/z 194 (M+, 29), 124 (10),
123 (100); HRMS: Calcd for C12H18S, m/z 194.1129;
found, m/z 194.1128.
CDCl3): d 7.38 (d, J 8.2 Hz, 2H), 7.18 (d, J 8.4 Hz,
2H), 3.05 (br s, 6H), 2.60 (t, J 7.6 Hz, 2H), 1.57–1.68
(m, 2H), 1.20–1.38 (m, 10H), 0.87 (t, J 6.8 Hz, 3H);
MS (70 eV): m/z 293 (M+, 13), 277 (5), 123 (4), 72
(100); HRMS: Calcd for C17H27NOS, m/z 293.1813;
found, m/z 293.1814.

J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
2365
3.12. p-Octylbenzenethiol (10c)
(M++Na, 29); HRFABMS: Calcd for C49H68O5S2Na,
m/z 823.4409 (M++Na); found, m/z 252.1551.
IR (CHCl3): 2920, 2855, 1493, 1466, 1119 cmÀ1; MS
(70 eV): m/z 222 (M+, 31), 125 (5), 123 (100); 1H
NMR (400 MHz, CDCl3): d 7.19 (d, J 8.4 Hz, 2H),
7.04 (d, J 8.0 Hz, 2H), 3.38 (s, 1H), 2.54 (t, J 7.6 Hz,
2H), 1.52–1.60 (m, 2H), 1.21–1.31 (m, 10H), 0.87 (t, J
6.8 Hz, 3H); HRMS: Calcd for C14H22S, m/z 222.1442;
found, m/z 222.1446; Anal. Calcd for C14H22S: C,
75.61; H, 9.97. Found: C, 76.15; H, 10.09.
3.15. (4-Octyl)benzyl 3,6-di-O-benzyl-2-deoxy-1,5-dithio-
L-threo-pentofuranoside (15a)
Methanesulfonyl chloride (48 lL, 0.63 mmol) was added
to a solution of 14a (204 mg, 0.255 mmol) in pyridine
(2 mL), and the reaction mixture was stirred for 4.5 h
at room temperature. After the reaction was complete,
the reaction was quenched with water and the mixture
was extracted with Et2O. The organic layer was succes-
sively washed with molar HCl and brine, dried over
MgSO4, and evaporated. The residue was dissolved in
DMF (10 mL), to which NaI (372 mg, 2.50 mmol) and
BaCO3 (740 mg, 3.75 mmol) were added, and the mix-
ture was stirred at 90 °C for 17.5 h. After the reaction
was complete, the mixture was filtered and partitioned
between Et2O and water. The organic layer was succes-
sively washed with aq sodium thiosulfate, water, and
brine, and then dried over MgSO4, and evaporated.
The residue was purified by silica gel column chroma-
tography (15:1 hexane–AcOEt) to afford 15a (89.8 mg,
64%) as a mixture of a and b isomers (a:b = 1:2). IR
3.13. p-Dodecylbenzenethiol (10d)
Dodecylbenzenesulfonyl chloride (90%, 5.0 g, Wako)8
was added to a solution of lithium aluminum hydride
(1.4 g, 36 mmol) in THF (100 mL) at 0 °C, and the reac-
tion mixture was refluxed for 22 h. After the reaction
was completed, the reaction was quenched with molar
HCl, and the mixture was extracted with AcOEt. The
organic layer was washed with brine, dried over MgSO4,
and evaporated. The residue was purified by silica gel
chromatography (hexane) to afford 10d (3.9 g, 97%
based on the calculation in which the starting material
was pure dodesylbenzenesulfonyl chloride).
1
(CHCl3): 3031, 2927, 2858, 1610, 1510 cmÀ1; H NMR
3.14. 3,4-Di-O-benzyl-2-deoxy-D-erythro-pentose
bis(4-octyloxy)benzyl dithioacetal (14a)
(400 MHz, CDCl3): d 7.37–7.18 (m, 10H), 6.84–6.78
(m, 2H), 4.59–4.45 (m, 5H), 4.31 (dd, J 8.1 and
4.0 Hz, 0.7H, b isomer), 4.26 (dd, J 7.3 and 6.2 Hz,
0.3H, a isomer), 4.19–4.15 (m, 0.7H, b isomer), 3.98–
3.82 (m, 3.3H), 3.79 (s, 0.7H, b), 3.77 (s, 0.3H, a isomer),
3.69–3.54 (m, 2H), 2.45 (ddd, A part of AB JAB 13.0 Hz,
J 6.0 and 4.3 Hz, 0.65H, b isomer), 2.32 (ddd, A part of
AB JAB 13.5 Hz, J 7.3 and 4.8 Hz, 0.35H), 2.23 (ddd, B
part of AB JAB 13.5 Hz, J 6.8 and 6.2 Hz, 0.35H, a iso-
mer), 1.92 (ddd, B part of AB JAB 13.0 Hz, J 8.2 and
3.6 Hz, 0.65H, b), 1.77 (quintet, J 7.1 Hz, 2H), 1.44
(quintet, J 7.2 Hz, 2H), 1.36–1.22 (m, 10H), 0.89 (t, J
7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): a isomer,
d 158.2, 138.2, 137.9, 130.0 (2C), 129.3, 128.3 (2C),
128.2 (2C), 127.8, 127.7, 127.6 (2C), 127.6 (2C), 114.5
(2C), 80.8 (2C), 73.4, 71.5, 70.4, 50.8, 47.4, 40.3, 36.6,
31.8, 29.3, 29.26, 29.22, 26.0, 22.6, 14.1; b isomer, d
158.3, 138.1, 138.0, 129.9 (2C), 129.4, 128.4 (2C),
128.3, 127.6 (4C), 127.6 (2C), 114.6 (2C), 80.7 (2C),
73.3, 71.6, 69.5, 68.0, 51.6, 48.7, 41.8, 36.5, 31.8, 31.8,
29.3, 29.26, 29.22, 26.0, 22.6, 14.1. FABMS: m/z 587
(M++Na, 2); HRFABMS: Calcd for C34H44O3S2Na,
(M++Na), m/z 587.2630; found m/z 587.2623.
p-Octyloxyphenylmethanethiol 6 (5.8 g, 23 mmol) and
concd HCl (2.1 mL) were added to methyl 3,5-di-O-benz-
yl-2-deoxy-a,b-D-erythro-pentofuranoside (13, 1.5 g,
4.6 mmol), and the reaction mixture was stirred at
40 °C for 18.5 h. After the reaction was complete, satd
aq NaHCO3 was added to the reaction mixture, which
was the extracted with Et2O. The organic layer was
washed with brine, dried over MgSO4, and evaporated.
The residue was purified by silica gel column chroma-
tography (12:1!8:1 hexane–AcOEt) to afford 14a
24
(3.1 g, 84%) as a colorless oil: ½aꢀD À69.44 (c 0.99,
CHCl3); 1H NMR (400 MHz, CDCl3): d 7.33–7.26
(arom, 8H), 7.16 (dt, J 8.8 and 2.6 Hz, 2H), 7.62–7.04
(m, 2H), 7.02–6.98 (m, 2H), 6.73–6.77 (m, 2H), 4.51 (s,
2H), 4.32 (d, A part of AB JAB 11.4 Hz, 1H), 4.06 (d,
B part of AB JAB 11.4 Hz, 1H), 3.88 (t, J 6.6 Hz, 2H),
3.85–3.61 (m, 9H), 3.48 (dd, A part of AB JAB 9.6 Hz,
J 5.9 Hz, 1H), 3.44 (dd, B part of AB JAB 9.6 Hz, J
4.2 Hz, 1H), 2.30 (d, J 4.2 Hz, 1H), 2.13 (ddd, A part
of AB JAB 14.7, J 9.9 and 3.9 Hz, 1H), 1.89 (ddd, B part
of AB JAB 14.7, J 10.9, 2.6 Hz, 1H), 1.81–1.69 (m, 4H),
1.51–1.28 (m, 20H), 0.89 (br t, J 6.8, 6H); 13C NMR
(100 MHz, CDCl3): d 158.1, 158.0, 138.3, 137.8, 130.2
(2C), 130.1 (2C), 130.0, 129.91, 128.5 (2C), 128.2 (2C),
127.83, 127.81, 127.6 (3C), 127.4, 114.4 (2C), 114.3
(2C), 77.2, 73.4, 72.7, 71.8, 70.7, 67.9, 67.8, 46.0, 37.2,
34.3, 33.4, 31.8 (2C), 29.4 (2C), 29.34, 29.31, 29.2 (2C),
26.09, 26.07, 22.6 (2C), 14.0 (2C); FABMS: 823
3.16. 4-Benzoyl-3,5-di-O-benzyl-2-deoxy-L-threo-pentose
bis(4-octyloxy)benzyl dithioacetal (16a)
A mixture of triphenylphosphine (151 mg, 0.58 mmol),
benzoic acid (71 mg, 0.58 mmol), and diisopropyl azo-
dicarboxylate (DIAD, 0.11 mL, 0.58 mmol) in THF

2366
J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
(1.5 mL) was added dropwise to a solution of 14a
(259 mg, 0.32 mmol) in THF (3.5 mL), and the reaction
mixture was stirred for 10 h. After the reaction was com-
plete, THF was evaporated, and the residue was purified
by silica gel column chromatography (15:1 hexane–
AcOEt) to afford compound 16a (240 mg, 83%) as a col-
4.8 Hz, 1H), 1.94 (ddd, B part of AB JAB 14.4 Hz, J
10.1 and 3.7 Hz, 1H), 1.76 (quintet, J 6.6 Hz, 2H),
1.65 (quintet, J 6.6 Hz, 2H), 1.46–1.29 (m, 20H), 0.89
(t, J 6.3 Hz, 3H), 0.88 (t, J 6.8 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d 158.12, 158.08, 138.3, 137.9,
130.2, 130.1, 129.9, 129.8, 128.4 (2C), 128.2 (2C), 127.8
(2C), 127.7, 127.6 (2C), 127.5 (2C), 114.4 (2C), 114.3
(2C), 76.6, 73.3, 73.2, 71.1, 68.7, 45.7, 37.7, 34.3, 33.7,
31.8 (2C), 29.4 (2C), 29.32, 29.31, 29.2 (2C), 26.1, 26.0,
22.7 (2C), 14.1 (2C). FABMS: m/z 823 (M++Na, 27);
HRFABMS: Calcd for C49H68O5S2Na (M++Na), m/z
823.4406; found, m/z 823.4412.
22:6
orless oil: ½aꢀD À76.25 (c 1.07, CHCl3); IR (CHCl3):
3024, 3010, 2927, 2856, 1716, 1608, 1500 cmÀ1 1H
;
NMR (400 MHz, CDCl3): d 8.06–8.03 (m, 2H), 7.57–
7.54 (m, 1H), 7.45–7.42 (m, 2H), 7.33–7.20 (m, 8H),
7.15–7.12 (m, 2H), 7.06–7.01 (m, 2H), 6.93–6.90 (m,
2H), 6.70–6.64 (m, 2H), 5.38 (ddd, J 6.2, 4.9, and
3.7 Hz, 1H), 4.53 (d, A part of AB JAB 12.1 Hz, 1H),
4.47 (d, B part of AB JAB 12.1 Hz, 1H), 4.44 (d, A part
of AB JAB 11.4 Hz, 1H), 4.07 (d, B part of AB JAB
11.4 Hz, 1H), 4.06–4.02 (m, 1H), 3.85 (t, J 6.7 Hz,
2H), 3.84–3.64 (m, 9H), 3.71 (d, A part of AB JAB
13.2 Hz, 1H), 3.53 (d, B part of AB JAB 13.2, 1H),
2.11 (ddd, A part of AB JAB 14.3 Hz, J 10.1, 3.7 Hz,
1H), 1.94 (ddd, A part of AB JAB 14.3 Hz, J 11.0 and
2.6 Hz, 1H), 1.77 (quintet, J 6.8 Hz, 2H), 1.73 (quintet,
J 6.6 Hz, 2H), 1.57–0.87 (m, 20H), 0.89 (t, J 6.0 Hz,
3H), 0.88 (t, J 6.6 Hz, 3H). 13C NMR (100 MHz,
CDCl3): d 165.8, 158.1, 138.2, 137.9, 133.0, 130.03
(2C), 130.01, 129.8, 129.7 (2C), 129.5, 128.3 (4C),
128.1 (2C), 127.6 (2C), 127.6 (2C), 127.5 (2C), 127.3
(2C), 114.4 (2C), 114.3 (2C), 75.4, 73.8, 73.3, 73.0,
68.1, 67.9, 67.8, 45.8, 37.3, 34.5, 33.4, 31.8 (2C), 29.4
(2C), 19.32 (2C), 29.31 (2C), 29.2, 26.1, 26.06 (2C),
22.6 (2C). FABMS: m/z 927 (M++Na, 1); HRFABMS:
Calcd for C56H72O6S2Na, m/z 927.4668, (M++Na);
found, m/z 927.4677.
3.18. O-4-Octyloxybenzyl 3,6-di-O-benzyl-2-deoxy-1,5-
dithio-D-erythro-pentofuranoside (17)
Methanesulfonyl chloride (0.35 mL, 4.6 mmol) was
added to a solution of 16b (1.46 g, 1.82 mmol) in pyr-
idine, and the reaction mixture was stirred at room tem-
perature for 1.5 h. After the reaction was complete, the
reaction was quenched with water and the mixture was
extracted with Et2O. The organic layer was successively
washed with molar HCl and brine, dried over MgSO4,
and evaporated. The residue was then dissolved in
DMF (85 mL), to which NaI (2.7 g, 11 mmol) and
BaCO3 (5.4 g, 27 mmol) were added and stirred at
90 °C for 17 h. After the reaction was complete, the
mixture was filtered, and the filtrate was partitioned
between Et2O and water. The organic layer was succes-
sively washed with aq sodium thiosulfate, water, and
brine, dried over MgSO4, and evaporated. The residue
was purified by silica gel column chromatography
(15:1 hexane–AcOEt) to afford 17 (1.01 g, 98%). The
isomers (a isomer, 127.0 mg; b isomer, 701.8 mg) were
separated by HPLC (5:1 hexane–AcOEt).
3.17. 3,5-Di-O-benzyl-2-deoxy-L-threo-pentose
bis(4-octyloxy)benzyl dithioacetal (16b)
21:9
3.18.1. a Isomer. Colorless oil: ½aꢀD +228.5 (c 0.62,
1
NaOMe in MeOH (28%, 0.26 mL, 1.28 mmol) was
added to a solution of 16a (583 mg, 0.64 mmol) in
MeOH (2 mL) and CHCl3 (2 mL) at 0 °C, and the reac-
tion mixture was stirred at room temperature for 15 h.
After the reaction was complete, the mixture was diluted
with 5% aq NaH2PO4 and extracted with Et2O. The or-
ganic layer was successively washed with satd aq NaH-
CO3 and brine, dried over MgSO4, and evaporated.
The residue was purified by silica gel column chroma-
tography (8:1!6:1 hexane–AcOEt) to afford 16b
CHCl3); IR (CHCl3): 2929, 2856, 1608, 1510 cmÀ1; H
NMR (400 MHz, CDCl3): d 7.36–7.25 (m, 10H), 7.23–
7.20 (m, 2H), 6.84–6.80 (m, 2H), 4.55 (d, A part of
AB JAB 12.3 Hz, 1H), 4.50 (s, 2H), 4.48 (d, B part of
AB JAB 12.3 Hz, 1H), 4.30 (dd, J 5.9 and 10 Hz, 1H),
4.40 (q, J 5.3 Hz, 2H), 3.92 (t, J 6.6 Hz, 2H), 3.82 (q,
J 5.5 Hz, 1H), 3.79 (s, 1H), 3.52 (dd, A part of AB
JAB 9.9 Hz, J 8.4 Hz, 1H), 3.47 (dd, B part of AB JAB
9.9 Hz, J 6.2 Hz, 1H), 2.43 (ddd, A part of AB JAB
13.5 Hz, J 6.9 and 5.1 Hz, 1H), 2.14 (ddd, B part of
AB JAB 13.5 Hz, J 5.8 and 5.7 Hz, 1H), 1.76 (quintet,
J 7.0 Hz, 2H), 1.48–1.26 (m, 10H), 0.89 (t, J 6.9 Hz,
3H); 13C NMR (100 MHz, CDCl3): d 158.2, 138.0,
137.9, 130.0 (2C), 129.3, 128.4 (2C), 128.3 (2C), 127.7
(2C), 127.64 (2C), 127.6 (2C), 114 (2C), 82.6, 73.1,
71.6, 71.5, 68.0, 53.0, 48.8, 40.9, 36.5, 31.8, 29.3, 29.26,
29.21, 26.0, 22.6, 14.1. FABMS: m/z 587 (M++Na,
31); HRFABMS: Calcd for C34H44O3S2Na (M++Na),
m/z 587.2630; found, m/z 587.2637.
27:6
(429 mg, 84%) as a colorless oil: ½aꢀD À62.15 (c 1.39,
CHCl3); IR (CHCl3): 3566, 3020, 2850, 1610,
1
1510 cmÀ1; H NMR (400 MHz, CDCl3): d 7.37–7.23
(m, 8H), 7.14–7.12 (m, 2H), 7.09–7.05 (m, 2H), 7.03–
7.00 (m, 2H), 6.73–6.68 (m, 4H), 4.48 (s, 2H), 4.25 (d,
A part of AB JAB 11.4 Hz, 1H), 4.10 (d, B part of AB
JAB 11.4 Hz, 1H), 3.87 (t, J 5.7 Hz, 2H), 3.83–3.63 (m,
9H), 3.42 (d, J 5.7 Hz, 2H), 2.29 (d, J 5.7 Hz, 1H),
2.14 (ddd, A part of AB JAB 14.4 Hz, J 9.0 and

J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
2367
22:3
3.18.2. b Isomer. Colorless oil: ½aꢀD +102.4 (c 0.78,
3.20. 4-Heptylphenyl 2,3,4,6-tetra-O-acetyl-1-thio-b-D-
glucopyranoside (19b)
CHCl3); IR (CHCl3): 2929, 2856, 1608, 1510 cmÀ1; H
1
NMR (400 MHz, CDCl3): d 7.36–7.25 (m, 10H), 7.22–
7.19 (m, 2H), 6.84–6.80 (m, 2H), 4.55–4.46 (m, 5H),
4.24 (dd, J 6.4, 3.7 Hz, 1H), 3.92 (t, J 6.6 Hz, 2H),
3.77 (dd, J 15.0, 13.4 Hz, 2H), 3.67 (ddd, J 8.6, 6.2,
and 2.6 Hz, 1H), 3.54–3.46 (m, 2H), 2.34 (ddd, A part
of AB JAB 13.5 Hz, J 5.31 and 3.13 Hz, 1H), 2.00
(ddd, B part of AB JAB 13.5 Hz, J 8.9 and 4.4 Hz,
1H), 1.77 (quintet, J 6.8 Hz, 2H), 1.44 (quintet, J
8.0 Hz, 2H), 1.36–1.18 (m, 8H), 0.89 (t, J 6.8 Hz, 3H);
13C NMR (100 MHz, CDCl3): d 158.3, 138.0, 137.9,
129.9 (2C), 129.4, 128.4 (4C), 83.0, 73.0, 71.0, 68.0,
53.1, 49.7, 41.2, 36.4, 31.8, 39.3, 29.3, 29.3, 26.0, 22.6,
14.1. FABMS: m/z 587 (M++Na, 73); HRFABMS:
Calcd for C34H44O3S2Na (M++Na), m/z 587.2630;
found, m/z 587.2637.
Mp 83.5–83.9 °C (hexane and Et2O); IR (CHCl3): 3032,
3013, 2932, 2858, 1755, 1369, 1246, 1215, 1042 cmÀ1; 1H
NMR (400 MHz, CDCl3): d 7.40 (d, J 8.1 Hz, 2H), 7.12
(d, J 8.1 Hz, 2H), 5.21 (t, J 9.3 Hz, 1H), 5.04 (t, J 9.8 Hz,
1H), 4.96 (dd, J 9.8, 9.3 Hz, 1H), 4.65 (d, J 10.1 Hz, 1H),
4.20 (d, J 4.9 Hz, 1H), 4.19 (d, J 2.7 Hz, 1H), 3.71 (ddd,
J 10.1, 4.9, 2.7 Hz, 1H), 2.59 (t, J 7.7 Hz, 2H), 2.09 (s,
3H), 2.08 (s, 3H), 2.02 (s, 3H), 1.99 (s, 3H), 1.60 (br t,
J 7.7 Hz, 2H), 1.36–1.22 (m, 8H), 0.88 (br t, J 6.9 Hz,
3H); FABMS: m/z 561 (M++Na, 90); HRFABMS:
Calcd for C27H38O9SNa, m/z 561.2134; found, m/z
561.2128.
3.21. Methyl 2,3,4,6-tetra-O-acetyl-D-glucopyranosyl-
(1!6)-2,3,4-tri-O-acetyl-a-D-glucopyranoside (21)
3.19. Dodecyl 2,3,4,6-tetra-O-acetyl-1-thio-D-gluco-
pyranoside (19a)
BF3ÆEt2O (51 lL, 0.40 mmol) and NIS (90 mg,
0.40 mmol) were added to a mixture of the a isomer of
19a (61.0 mg, 0.10 mmol), methyl 2,3,4-tri-O-acetyl-a-
Dodecanethiol (735 lL, 3.07 mmol) and BF3ÆEt2O
(1.6 mL, 12.8 mmol) were added to a solution of per-
O-acetylated D-glucose (1.0 g, 2.6 mmol) in CH2Cl2
(5.0 mL), and the reaction mixture was stirred at room
temperature for 6 h. After the reaction was complete,
the organic solvent was removed in vacuo, and the res-
idue was purified by silica gel chromatography (3:1 hex-
ane–AcOEt) to give 19a as a mixture of a and b
isomers.9
˚
D-glucopyranoside (20) (35.0 mg, 0.10 mmol), and 4 A
molecular sieves (20 mg) in CH2Cl2 (2.0 mL), and the
reaction mixture was stirred for 5 min at room tempera-
ture. After the reaction, satd aq NaHCO3, and satd aq
NaS2O3 were successively added, and the solvent was
removed in vacuo. The residue was purified by silica
gel column chromatography (20:1 CHCl3–acetone) to
afford 21 (57 mg, 87%).10
3.19.1. a Isomer. IR (CHCl3): 3036, 2928, 2855, 1747,
Acknowledgments
1601, 1369, 1242, 1038 cmÀ1 1H NMR (400 MHz,
;
CDCl3): d 5.65 (d, J 5.9 Hz, 1H), 5.37 (t, J 9.7 Hz,
1H), 5.05 (dd, J 10.2, 9.7 Hz, 1H), 5.02 (dd, J 10.2,
5.9 Hz, 1H), 4.43 (ddd, J 9.7, 4.7, 2.3 Hz, 1H), 4.30
(dd, A part of AB J 12.4, 4.7 Hz, 1H), 4.07 (dd, B
part of AB J 12.4, 2.3 Hz, 1H), 2.60–2.45 (m, 2H),
2.09 (s, 3H), 2.07 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H),
1.64–1.52 (m, 2H), 1.35–1.15 (m, 18H), 0.88 (t, J
6.9 Hz, 3H); FABMS: m/z 538 (M++Na, 36);
HRFABMS: Calcd for C26H44O9SNa, m/z 555.2604;
found, m/z 555.2610.
This research was financially supported in part by the
Frontier Research Program and the 21st Century Center
of Excellence Program ꢂDevelopment of Drug Discovery
Frontier Integrated from Tradition to Proteomeꢃ of the
Ministry of Education, Culture, Sport and Technology,
Japan.
References
1. See, for example, Glycoscience; Fraser-Reid, B., Tatsuta,
K., Thiem, J., Eds.; Springer: New York, 2001.
3.19.2. b Isomer.9 IR (CHCl3): 3020, 2928, 2855, 1755,
2. (a) Yoshikawa, M.; Morikawa, T.; Matsuda, H.; Tanabe,
G.; Muraoka, O. Bioorg. Med. Chem. 2002, 10, 1547–
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3. (a) Ferrier, R. J.; Furneaux, R. H. Methods Carbohydr.
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Chem. Soc. 1983, 105, 2430; (e) Lonn, H. J. Carbohydr.
1
1601, 1369, 1238 cmÀ1; H NMR (400 MHz, CDCl3): d
5.22 (t, J 9.5 Hz, 1H), 5.09 (d, J 9.5 Hz, 1H), 5.03 (dd, J
10.1, 9.5 Hz, 1H), 4.48 (d, J 10.1 Hz, 1H), 4.24 (dd, A
part of AB J 12.5, 4.9 Hz, 1H), 4.14 (dd, B part of AB
J 12.5, 2.4 Hz, 1H), 3.70 (ddd, J 9.5, 4.9, 2.4 Hz, 1H),
2.73–2.60 (m, 2H), 2.08 (s, 3H), 2.07 (s, 3H), 2.03 (s,
3H), 2.01 (s, 3H), 1.64–1.51 (m, 2H), 1.33–1.19 (m,
18H), 0.88 (t, J 6.9 Hz, 3H); FABMS: m/z 555
(M++Na, 14); HRFABMS: Calcd for C26H44O9SNa,
m/z 555.2604; found, m/z 555.2611.

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J. Hasegawa et al. / Carbohydrate Research 340 (2005) 2360–2368
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