9410
B. Yu et al. / Tetrahedron 57 ,2001) 9403±9413
J14.0, 6.3 Hz); ESIMS m/z: 1096 <M1Na). Anal. Calcd
1440, 1372, 1244, 1222, 1082, 1070, 1040 cm21; dH <300
MHz, CDCl3) 7.46±7.19 <m, 5H), 5.44 <t, 1H, J9.3 Hz),
5.22 <dd, 1H, J10.2, 3.0 Hz), 5.15 <m, 1H), 5.04 <t, 1H,
J9.9, 10.2 Hz), 4.86 <m, 2H), 4.80 <dd, 1H, J10.2,
3.7 Hz), 3.98 <m, 1H), 3.86 <dd, 1H, J9.9, 6.3 Hz), 3.73
<t, 1H, J9.6 Hz), 3.52 <dd, 1H, J13.5, 2.5 Hz), 3.39 <s,
3H), 3.12 <dd, 1H, J13.5, 7.7 Hz), 2.14, 2.06, 2.05, 2.00
<each s, each 3H), 1.15 <d, 3H, J6.3 Hz); EIMS m/z: 642,
611, 582, 511, 398, 353, 273. Anal. Calcd for C29H38O14S:
C, 54.19; H, 5.96. Found: C, 53.87, H, 6.14.
for C61H52O16S: C, 68.27; H, 4.88. Found: C, 68.33; H, 5.17.
4.4.6. Cholesterol-3-yl 2,3,4-tri-O-benzoyl-6-S-phenyl-6-
thio-b-d-galactopyranoside -33). Chromatography with
petroleum ether±EtOAc <10:1) afforded 33 as a white
28
amorphous solid <94%): [a]D 190.6 <c 0.66, CHCl3);
n
max<KBr) 2938, 1728, 1452, 1285, 1263, 1093 cm21; dH
<300 MHz, CDCl3) 8.10±7.21 <m, 20H), 5.94 <d, 1H,
J3.0 Hz), 5.73 <dd, 1H, J10.3, 7.8 Hz), 5.52 <dd, 1H,
J10.4, 3.3 Hz), 5.25 <d, 1H, J4.7 Hz), 4.82 <d, 1H, J
8.0 Hz), 3.98 <t, 1H, J6.6 Hz), 3.56 <m, 1H), 3.27 <dd, 1H,
J14.2, 7.6 Hz), 3.13 <dd, 1H, J14.0, 5.8 Hz); EIMS m/z:
831, 584, 567, 444, 368, 105. Anal. Calcd for C60H72O8S: C,
75.60; H, 7.61. Found: C, 75.77; H, 7.55.
4.5.4. Methyl 3,4-O-isopropylidene-6-S-phenyl-6-thio-2-
O--2,3,4,6-tetra-O-benzoyl-b-d-glucopyranosyl)-b-d-
galactopyranoside -37). Chromatography with petroleum
ether±EtOAc <5:1) afforded 37 as a white foam <99%):
25
[a]D 114.8 <c 1.04, CHCl3); nmax<KBr) 3375, 3246,
2987, 1732, 1602, 1452, 1267, 1110, 1069 cm21; dH
<300 MHz, CDCl3) 8.01±7.21 <m, 25H), 5.91 <t, 1H, J
9.6 Hz), 5.70 <t, 1H, J9.9 Hz), 5.54 <t, 1H, J9.3 Hz),
5.24 <d, 1H, J8.0 Hz), 4.66 <dd, 1H, J12.1, 3.3 Hz),
4.52 <dd, 1H, J12.1, 5.2 Hz), 4.17 <m, 2H), 4.08 <dd,
1H, J5.6, 1.8 Hz), 3.99 <t, 1H, J6.1 Hz), 3.69 <m, 2H),
3.49 <s, 3H), 3.25 <m, 2H), 1.18 and 1.11 <each s, each 3H);
EIMS m/z: 905, 904, 844, 579, 105. Anal. Calcd for
C50H48O14´0.5H2O: C, 65.71; H, 5.40. Found: C, 65.87; H,
5.25.
4.5. Procedure for preparation of 34±40
A suspension of the trichloroacetimidate donor <21±23 or
Ê
17, 2.10 mmol), acceptor <9 or 11, 1.05 mmol), and 4 A MS
<2.0 g) in dry CH2Cl2 <15 mL) was stirred at room tempera-
ture for 30 min and then cooled to 2508C. A solution of
TMSOTf <1.0 mL, 0.21 M) in CH2Cl2 was slowly added to
the reaction. After being stirred for another 30 min, the
reaction was quenched with triethylamine <0.2 mL) and
®ltered. The ®ltrates were concentrated in vacuo to give a
residue, which was puri®ed by ¯ash column chroma-
tography.
4.5.5. Methyl 3,4-O-isopropylidene-6-S-phenyl-6-thio-2-
O--2,3,4-tri-O-acetyl-a-l-rhamnopyranosyl)-b-d-galacto-
pyranoside -38). Chromatography with petroleum ether±
EtOAc <5:1±3:1) afforded 38 as a white foam <99%):
4.5.1. Methyl 2,3-di-O-acetyl-6-S-phenyl-6-thio-4-O-
-2,3,4,6-tetra-O-benzoyl-b-d-glucopyranosyl)-a-d-gluco-
pyranoside -34). Chromatography with petroleum ether±
EtOAc <3:1) afforded 34 as a colorless syrup <70%):
25
[a]D 241.9 <c 1.13, CHCl3); nmax<KBr) 2989, 2940,
1750, 1373, 1224, 1137, 1077, 1048 cm21; dH <300 MHz,
CDCl3) 7.42±7.21 <m, 5H), 5.31 <m, 1H), 5.24 <dd, 1H,
J10.0, 3.6 Hz), 5.17 <s, br, 1H), 5.06 <t, 1H, J9.9 Hz),
4.17 <m, 4H), 3.80 <td, 1H, J6.9, 1.7 Hz), 3.68 <t, 1H,
J6.9 Hz), 3.53 <s, 3H), 3.32 <m, 2H), 2.15, 2.06 and 1.98
<each s, each 3H), 1.50 and 1.27 <each s, each 3H), 1.18 <d,
3H, J6.3 Hz); EIMS m/z: 598, 567, 538, 273, 153; HRMS
m/z Calcd for C28H38O12S: 598.16344. Found: 598.20774.
Anal. Calcd for C28H38O12S´2.5H2O: C, 52.25; H, 6.73.
Found: C, 52.13, H, 6.81.
13
[a]D 171.5 <c 1.22, CHCl3); nmax<neat) 3064, 1736,
1602, 1585, 1452, 1371, 1316, 1267, 1178, 1094, 1069,
1027 cm21; dH <300 MHz, CDCl3) 8.07±7.21 <m, 25H),
5.72 <t, 1H, J9.6 Hz), 5.60 <t, 1H, J9.6 Hz), 5.49 <t,
2H, J9.3, 8.2 Hz), 4.82 <m, 3H), 4.64 <dd, 1H, J12.1,
3.0 Hz), 4.43 <dd, 1H, J12.4, 5.5 Hz), 3.98 <m, 1H), 3.88
<m, 2H), 3.41 <d, 1H, J10.2 Hz), 3.29 <s, 3H), 3.11 <dd,
1H, J13.5, 5.0 Hz), 2.05 and 1.97 <each s, each 3H); EIMS
m/z: 948, 826, 579, 370,105. Anal. Calcd for C51H48O16S: C,
64.55; H, 5.10. Found: C, 64.30, H, 5.14.
4.5.6. Methyl 3,4-O-isopropylidene-6-S-phenyl-6-thio-2-
O--2,3,4-tri-O-benzoyl-6-S-phenyl-6-thio-b-d-galacto-
pyranosyl)-b-d-galactopyranoside -39). Chromatography
with petroleum ether±EtOAc <5:1) afforded 39 as a white
4.5.2. Methyl 2,3-di-O-acetyl-6-S-phenyl-6-thio-4-O-
-2,3,4,6-tetra-O-acetyl-a-d-mannopyranosyl)-a-d-gluco-
pyranoside -35). Chromatography with petroleum ether±
EtOAc <2:1) afforded 35 as a colorless syrup <81%):
25
foam <99%): [a]D 160.8 <c 0.98, CHCl3); nmax<KBr)
1732, 1602, 1452, 1283, 1263, 1069, 1026 cm21; dH
<300 MHz, CDCl3) 8.10±7.21 <m, 25H), 5.98 <d, 1H,
J3.3 Hz), 5.75 <dd, 1H, J10.4, 8.0 Hz), 5.56 <dd, 1H,
J10.4, 3.3 Hz), 5.08 <d, 1H, J8.2 Hz), 4.22 <d, 1H,
J8.0 Hz), 4.02 <m, 3H), 3.68 <m, 2H), 3.55 <s, 3H),
3.33±3.10 <m, 4H), 1.11 and 1.07 <each s, each 3H);
EIMS m/z: 892, 861, 783, 567, 105. Anal. Calcd for
C49H48O12S2: C, 65.90; H, 5.42. Found: C, 65.89, H, 5.25.
25
[a]D 186.3 <c 0.86, CHCl3); nmax<neat) 2945, 1751,
1584, 1483, 1440, 1372, 1228, 1190, 1118 cm21; dH
<300 MHz, CDCl3) 7.41±7.18 <m, 5H), 5.51 <d, 1H, J
2.5 Hz), 5.29 <m, 3H), 5.10 <dd, 1H, J9.9, 4.9 Hz), 4.82
<m, 2H), 4.71 <m, 1H), 4.25 <dd, 1H, J12.1, 4.4 Hz), 4.12
<dd, 1H, J12.1, 2.7 Hz), 3.86 <m, 1H), 3.59 <m, 2H), 3.36
<s, 3H), 2.96 <dd, 1H, J14.2, 8.4 Hz); EIMS m/z: 700, 370,
353, 331, 169. Anal. Calcd for C31H40O16S: C, 53.14; H,
5.75. Found: C, 52.85, H, 5.96.
4.5.7. Methyl 2,3-di-O-acetyl-6-S-phenyl-6-thio-4-O-
-2,3,4-tri-O-benzoyl-6-S-phenyl-6-thio-b-d-galactopyrano-
syl)-a-d-glucopyranoside -40). Chromatography with
petroleum ether±EtOAc <4:1) afforded 40 as a white foam
4.5.3. Methyl 2,3-di-O-acetyl-6-S-phenyl-6-thio-4-O-
-2,3,4-tri-O-acetyl-a-l-rhamnopyranosyl)-a-d-gluco-
pyranoside -36). Chromatography with petroleum ether±
EtOAc <4:1±3:1) afforded 36 as a colorless syrup <92%):
[a]D 138.9 <c 1.17, CHCl3); nmax<neat) 2987, 1750,
25
<83%): [a]D 174.5 <c 1.00, CHCl3); nmax<KBr) 3063,
1733, 1452, 1282, 1245, 1027 cm21; dH <300 MHz,
29