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F. Chery et al. / Tetrahedron 62 (2006) 5141–5151
5148
4.7.2. Methyl 2,3-di-O-benzyl-6-S-[(Z)-20-(phenylsul-
fonyl)-vinyl]-6-thio-a-D-glucopyranoside (12aZ). Obtained
from 4a and Z-BPSE; silica gel column chromatography
(petroleum ether/AcOEt 7:3, 65:35, then 6:4) afforded com-
pound 12aZ with 91% yield as a colourless gum, [a]D +26
4.7.5. Methyl 2,3-di-O-benzyl-4-S-[(E)-20-(phenylsul-
fonyl)-vinyl]-4-thio-a-D-glucopyranoside (13aE). Obtained
from 9a and E-BPSE; silica gel column chromatography
(petroleum ether/AcOEt 7:3, 65:35, then 6:4) afforded
13aE with 76% yield as a colourless gum, [a]D +38 (c 1.5,
(c 2.0, CHCl3). 1H NMR d 2.77 (dd, 1H, J5–6b¼8.3, J6a–6b
¼
CHCl3). 1H NMR d 2.45 (br s, 1H, OH), 3.25 (t, 1H, J3–4
J4–5¼10.8, H-4), 3.36 (s, 3H, OMe), 3.52 (dd, 1H, J1–2
¼
14.7, H-6b), 2.91 (br s, 1H, OH), 3.12 (br d, 1H, J5–6a<0.5,
H-6a), 3.14 (s, 3H, OMe), 3.26–3.37 (m, 1H, H-4), 3.43
(dd, 1H, J2–3¼9.6, H-2), 3.64 (br t, 1H, J4–5¼9.6, H-5),
3.72 (t, 1H, J3–4¼9.6, H-3), 4.53 (d, 1H, J1–2¼3.6, H-1),
4.60 and 4.69 (2d, AB system, 2H, Jgem¼12.1, PhCH2O),
4.71 and 4.96 (2d, AB system, 2H, Jgem¼11.5, PhCH2O),
6.16 (d, 1H, Jvic¼10.2, H-20), 7.21 (d, 1H, H-10), 7.28–7.35
(m, H–Ar), 7.48 (m, 2H, meta-H–PhSO2), 7.86 (m, 1H,
para-H–PhSO2), 7.95 (d, 2H, Jvic¼7.7, ortho-H–PhSO2).
13C NMR d 37.2 (C-6), 56.5 (OMe), 72.4 (C-5), 73.5 (C-4),
74.0 and 76.3 (PhCH2O), 80.5 (C-2), 82.1 (C-3), 98.8
(C-1), 122.8 (C-20), 128.1–130.8 (CH–Ar), 139.0 and 139.8
(2*CIV–Ar), 142.4 (CIV–PhSO2), 149.9 (C-10). MS IS m/z¼
579.5 [M+Na]+, 595.5 [M+K]+. HRMS: C29H32O7S2: calcd
556.1589; found 556.1583.
¼
3.4, J2–3¼9.2, H-2), 3.64–3.79 (m, 3H, H-5, H-6a, H-6b),
3.84 (t, 1H, H-3), 4.60 and 4.74 (2d, AB system, 2H,
Jgem¼12.2, PhCH2O), 4.63 (d, 1H, H-1), 4.71 and 4.87 (2d,
AB system, 2H, Jgem¼10.9, PhCH2O), 6.45 (d, 1H, Jvic¼14.7,
H-20), 7.25–7.34 (m, H–Ar), 7.45 (br t, 2H, meta-H–PhSO2),
7.55 (br t, 1H, Jvic¼7.3, para-H–PhSO2), 7.80 (d, 2H,
Jvic¼7.3, ortho-H–PhSO2), 7.83 (d, 1H, H-10). 13C NMR
d 50.1 (C-4), 56.1 (OMe), 62.2 (C-6), 71.2 (C-5), 73.8 and
76.6 (PhCH2O), 79.1 (C-3), 81.2 (C-2), 98.8 (C-1), 123.9
(C-20), 127.8–129.7 (CH–Ar), 133.6 (CH–para-PhSO2),
138.3 and 138.5 (2*CIV–Ar), 141.5 (CIV–PhSO2), 145.5
(C-10). MS IS m/z¼525.5 [MꢁOMe]+, 557.5 [M+H]+,
574.5 [M+NH4]+. HRMS: C29H32O7S2: calcd 556.1589;
found 556.1591.
4.7.3. Methyl 2,3-di-O-benzyl-6-S-[(E)-20-(phenylsul-
fonyl)-vinyl]-6-thio-b-D-glucopyranoside (12bE). Obtained
from 4b and E-BPSE; silica gel column chromatography
(petroleum ether/AcOEt 7:3, then 6:4) afforded compound
12bE with 70% yield as a colourless gum, [a]D ꢁ13 (c 4.1,
4.7.6. Methyl 2,3-di-O-benzyl-4-S-[(Z)-20-(phenylsul-
fonyl)-vinyl]-4-thio-a-D-glucopyranoside (13aZ). Obtained
from 9a and Z-BPSE; silica gel column chromatography
(petroleum ether/AcOEt 6:4, 55:45, then 1:1) afforded 13aZ
with 92% yield as a colourless gum, [a]D +9 (c 1.9, CHCl3).
CHCl3). 1H NMR d 2.66 (br s, 1H, OH), 2.91 (dd, 1H, J5–6b
¼
1H NMR d 1.95 (br s, 1H, OH), 3.08 (t, 1H, J3–4¼J4–5
¼
6.8, J6a–6b¼14.1, H-6b), 3.23 (br d, 1H, J5–6a<0.5, H-6a),
3.34–3.40 (m, 4H, H-2, H-3, H-4, H-5), 3.48 (s, 3H, OMe),
4.28 (br d, 1H, J1–2¼6.8, H-1), 4.64 and 4.91 (2d, AB system,
2H, Jgem¼11.1, PhCH2O), 4.67 and 4.93 (2d, AB system, 2H,
Jgem¼11.3, PhCH2O), 6.29 (d, 1H, H-20, Jvic¼14.7), 7.23–
7.36 (m, H–Ar), 7.47 (t, 2H, meta-H–Ar PhSO2), 7.56 (t,
1H, para-H–PhSO2), 7.80 (d, 1H, H-10), 7.84 (d, 2H, ortho-
H–PhSO2, Jvic¼7.5). 13C NMR d 34.4 (C-6), 57.1 (OMe),
72.6 (C-4), 74.6 and 75.2 (PhCH2O), 74.7 (C-5), 82.2 (C-2),
83.8 (C-3), 104.7 (C-1), 121.8 (C-20), 127.3–129.2 (CH–
Ar), 133.1 (CH–para-PhSO2), 138.3 (2*CIV–Ar), 141.2
(CIV–PhSO2), 146.5 (C-10). MS IS m/z¼525.5 [MꢁOMe]+,
574.5 [M+NH4]+, 579.5 [M+Na]+, 595.5 [M+K]+. HRMS:
C29H32O7S2: calcd 556.1589; found 556.1580.
10.7, H-4), 3.38 (s, 3H, OMe), 3.48 (dd, 1H, J1–2¼3.4,
J2–3¼9.4, H-2), 3.72 (dt, 1H, J5–6a¼J5–6b¼2.3, H-5), 3.79–
3.85 (m, 2H, H-6a, H-6b), 3.87 (br t, 1H, H-3), 4.56 and
4.84 (2d, AB system, 2H, Jgem¼10.2, PhCH2O), 4.62 (d,
1H, H-1), 4.63 and 4.77 (2d, AB system, 2H, Jgem¼12.0,
PhCH2O), 6.14 (d, 1H, Jvic¼10.2, H-20), 7.13–7.37 (m, H-10,
H–Ar), 7.45 (br t, 2H, meta-H–PhSO2), 7.57 (br t, 1H,
Jvic¼7.4, para-H–PhSO2), 7.95 (d, 2H, Jvic¼7.6, ortho-H–
PhSO2). 13C NMR d 52.3 (C-4), 55.7 (OMe), 61.9 (C-6),
70.6 (C-5), 73.4 and 76.4 (PhCH2O), 79.3 (C-3), 80.7 (C-2),
98.5 (C-1), 122.7 (C-20), 127.2–129.2 (CH–Ar), 133.6 (CH–
para-PhSO2), 137.9 (2*CIV–Ar), 141.4 (CIV–PhSO2), 145.8
(C-10). MS IS m/z¼525.5 [MꢁOMe]+, 557.5 [M+H]+, 574.5
[M+NH4]+. HRMS: C29H32O7S2: calcd 556.1589; found
556.1575.
4.7.4. Methyl 2,3-di-O-benzyl-6-S-[(Z)-20-(phenylsul-
fonyl)-vinyl]-6-thio-b-D-glucopyranoside (12bZ). Obtained
from 4b and Z-BPSE; silica gel column chromatography
(petroleum ether/AcOEt 7:3, 6:4, then 1:1) afforded com-
pound 12bZ with 72% yield as a colourless gum, [a]D +43
4.7.7. Methyl 2,3-di-O-benzyl-4-S-[(E)-20-(phenylsul-
fonyl)-vinyl]-4-thio-b-D-glucopyranoside (13bE). Obtained
from 9b and E-BPSE; silica gel column chromatography
(petroleum ether/AcOEt 7:3, 65:35, then 6:4) afforded 13bE
with 96% yield as a colourless gum, [a]D +62 (c 1, CHCl3).
1
(c 3.6, CHCl3). H NMR d 2.63 (br s, 1H, OH), 2.80 (dd,
1H, J5–6b¼7.7, J6a–6b¼14.7, H-6b), 3.21 (br d, 1H, J5–6a
<
1H NMR d 2.55 (br s, 1H, OH), 3.28 (t, 1H, J3–4¼J4–5
¼
0.5, H-6a), 3.29–3.53 (m, 4H, H-2, H-3, H-4, H-5), 3.56 (s,
3H, OMe), 4.22 (d, 1H, J1–2¼7.2, H-1), 4.63 and 4.88 (2d,
AB system, 2H, Jgem¼11.5, PhCH2O), 4.69 and 4.93 (2d,
AB system, 2H, Jgem¼11.7, PhCH2O), 6.16 (d, 1H, Jvic J¼
10.4, H-20), 7.23–7.36 (m, H–Ar, H-10), 7.48 (m, 2H, meta-
H–Ar PhSO2), 7.88 (m, 1H, para-H–PhSO2), 7.96 (d, 2H,
Jvic¼7.7, ortho-H–PhSO2). 13C NMR d 37.4 (C-6), 57.3
(OMe), 72.3 (C-4), 75.1 and 75.2 (PhCH2O), 75.8 (C-5),
81.7 (C-2), 83.4 (C-3), 104.7 (C-1), 121.7 (C-20), 127.1–129.5
(CH–Ar), 133.4 (CH–para-PhSO2), 138.3 (2*CIV–Ar), 141.4
(CIV–PhSO2), 149.0 (C-10). MS IS m/z¼525.5 [MꢁOMe]+,
574.5 [M+NH4]+, 579.5 [M+Na]+, 595.5 [M+K]+. HRMS:
C29H32O7S2: calcd 556.1589; found 556.1594.
10.4, H-4), 3.35–3.55 (m, 3H, H-2, H-3, H-5), 3.54 (s, 3H,
OMe), 3.74 (d, 1H, J5–6b<0.5, H-6b), 3.91 (br d, 1H, J5–6a<
0.5, J6a–6b¼12.0, H-6a), 4.33 (d, 1H, J1–2¼7.7, H-1), 4.66
and 4.89 (2d, AB system, 2H, Jgem¼11.1, PhCH2O), 4.69
and 4.83 (2d, AB system, 2H, Jgem¼10.9, PhCH2O), 6.43 (d,
1H, Jvic¼14.7, H-20), 7.19–7.32 (m, H–Ar), 7.41 (br t, 2H,
meta-H–PhSO2), 7.52 (br t, 1H, Jvic¼7.2, para-H–PhSO2),
7.78 (d, 2H, Jvic¼7.1, ortho-H–PhSO2), 7.82 (d, 1H, H-10).
13C NMR d 49.5 (C-4), 57.3 (OMe), 61.8 (C-6), 74.8 and
75.9 (PhCH2O), 75.1 (C-5), 81.7 (C-3), 83.0 (C-2), 104.5
(C-1), 123.7 (C-20), 127.3–129.5 (CH–Ar), 133.1 (CH–para-
PhSO2), 137.7 and 138.1 (2*CIV–Ar), 140.9 (CIV–PhSO2),
144.8 (C-10). MS IS m/z¼525.5 [MꢁOMe]+, 557.5 [M+H]+,