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Q. Tian et al. / Tetrahedron 63 (2007) 2142–2147
d 1.95, 1.99, 2.01, 2.04 (4ꢃs, each 3H), 3.45 (t, J¼9.6 Hz,
1H), 3.52 (dd, J¼3.6, 9.6 Hz, 1H), 3.62–3.66 (m, 1H), 3.69
(dd, J¼4.4, 10.4 Hz, 1H), 3.81 (dd, J¼2.8, 10.0 Hz, 1H),
3.98 (dd, J¼6.4, 12.4 Hz, 1H), 4.00 (t, J¼9.2 Hz, 1H), 4.04
(dd, J¼1.2, 10.4 Hz, 1H), 4.10–4.16 (m, 2H), 4.23 (dd, J¼
4.8, 12.4 Hz, 1H), 4.50 (d, J¼7.6 Hz, 1H), 4.52 (d, J¼
10.8 Hz, 1H), 4.64 (d, J¼12.0 Hz, 1H), 4.75 (d, J¼12.8 Hz,
1H), 4.78 (d, J¼3.2 Hz, 1H), 4.80 (d, J¼11.2 Hz, 1H), 4.86
(d, J¼10.8 Hz, 1H), 5.00 (d, J¼10.8 Hz, 1H), 5.05 (dd,
J¼8.0, 9.6 Hz, 1H), 5.08 (t, J¼10.0 Hz, 1H), 5.17 (t,
J¼9.6 Hz, 1H), 5.21 (d, J¼10.4 Hz, 1H), 5.32 (dd, J¼1.2,
17.2 Hz, 1H), 5.86–5.96 (m, 1H), 7.25–7.35 (m, 15H); 13C
NMR (CDCl3, 100 MHz): d 170.7, 170.2, 169.3, 168.9,
138.8, 138.5, 138.1, 133.6, 128.4, 128.4, 128.3, 128.0,
127.8, 127.7, 127.5, 118.2, 100.6, 95.4, 81.9, 79.8, 77.6,
75.6, 74.9, 73.1, 73.0, 71.8, 71.3, 69.8, 68.4, 68.1, 68.0,
61.9, 20.6, 20.6, 20.5, 20.5; HR ESI-MS: m/z calcd for
C44H52O15 [M+Na]+: 843.3204; found: 843.3195.
4.2.4. Methyl N-[(tert-butoxy)carbonyl]-L-serine 2,3,4,6-
tetra-O-acetyl-b-D-galactopyranoside (26). Colorless
syrup; Rf 0.13 (petroleum ether/EtOAc, 3:1); [a]2D1 +7.7
(c 0.5, CHCl3); 1H NMR (CDCl3, 400 MHz): d 1.45
(s, 9H), 1.97, 2.04, 2.10, 2.14 (4ꢃs, each 3H), 3.75 (s, 3H),
3.84 (dd, J¼3.2, 10.4 Hz, 1H), 3.88 (t, J¼6.4 Hz, 1H),
4.08–4.15 (m, 2H), 4.25 (dd, J¼2.4, 10.0 Hz, 1H), 4.39–
4.41 (m, 1H), 4.47 (d, J¼8.0 Hz, 1H), 5.00 (dd, J¼3.2,
10.4 Hz, 1H), 5.16 (dd, J¼8.0, 10.4 Hz, 1H), 5.30 (d,
J¼7.2 Hz, 1H), 5.37 (d, J¼2.8 Hz, 1H); 13C NMR (CDCl3,
100 MHz): d 170.5, 170.0, 169.8, 169.5, 101.7, 70.8, 70.7,
69.6, 68.5, 66.8, 61.0, 53.8, 52.5, 50.2, 28.2, 20.6, 20.6,
20.5, 20.5; HR ESI-MS: m/z calcd for C23H35NO14
[M+Na]+: 572.1955; found: 572.1971.
4.2.5. 1,2:3,4-Di-O-isopropylidene-6-thio-(20,30,40,60-
tetra-O-acetyl-b-D-glucopyranosyl)-a-D-galactopyrano-
side (28). Colorless syrup; Rf 0.22 (petroleum ether/EtOAc,
3:1); [a]2D1 ꢀ39.2 (c 1.0, CHCl3); 1H NMR (CDCl3,
400 MHz): d 1.33, 1.34, 1.45, 1.53 (4ꢃs, each 3H), 2.00,
2.02, 2.05, 2.08 (4ꢃs, each 3H), 2.80 (dd, J¼6.0, 14.0 Hz,
1H), 2.98 (dd, J¼7.2, 14.0 Hz, 1H), 3.67–3.72 (m, 1H),
3.90 (t, J¼7.6 Hz, 1H), 4.07–4.14 (m, 2H), 4.24 (dd,
J¼5.2, 12.4 Hz, 1H), 4.29–4.31 (m, 1H), 4.61 (dd, J¼2.4,
8.0 Hz, 1H), 4.70 (d, J¼10.0 Hz, 1H), 5.00 (t, J¼9.2 Hz,
1H), 5.07 (t, J¼9.6 Hz, 1H), 5.22 (t, J¼9.2 Hz, 1H), 5.51
(d, J¼4.8 Hz, 1H); 13C NMR (CDCl3, 100 MHz): d 170.5,
170.1, 169.3, 169.3, 109.3, 108.6, 96.4, 83.8, 75.8, 73.9,
71.7, 70.8, 70.3, 70.1, 68.9, 68.4, 62.1, 26.0, 25.9, 24.8,
24.5, 20.6, 20.6, 20.5, 20.5; HR ESI-MS: m/z calcd for
C26H38O14S [M+Na]+: 629.1880; found: 629.1867.
4.2.2. Allyl 2,3,4-tri-O-benzyl-6-O-(20,30,40,60-tetra-O-
acetyl-b-D-galactopyranosyl)-a-D-glucopyranoside (18).
Colorless syrup; Rf 0.24 (petroleum ether/EtOAc, 3:1);
1
[a]2D1 +1.0 (c 3.5, CHCl3); H NMR (CDCl3, 400 MHz):
d 1.96, 1.96, 2.01, 2.11 (4ꢃs, each 3H), 3.44 (t, J¼9.6 Hz,
1H), 3.53 (dd, J¼3.6, 9.6 Hz, 1H), 3.68 (dd, J¼4.8,
10.8 Hz, 1H), 3.81–3.87 (m, 2H), 3.97 (dd, J¼5.6, 13.2 Hz,
1H), 4.01 (t, J¼9.2 Hz, 1H), 4.07–4.17 (m, 4H), 4.46 (d,
J¼8.0 Hz, 1H), 4.53 (d, J¼10.8 Hz, 1H), 4.63 (d, J¼
12.0 Hz, 1H), 4.75 (d, J¼12.0 Hz, 1H), 4.79 (d, J¼3.2 Hz,
1H), 4.81 (d, J¼10.8 Hz, 1H), 4.86 (d, J¼11.2 Hz, 1H),
4.98 (dd, J¼3.6, 10.4 Hz, 1H), 5.00 (d, J¼10.8 Hz, 1H),
5.20 (d, J¼10.4 Hz, 1H), 5.27 (d, J¼18.4 Hz, 1H), 5.30
(dd, J¼1.6, 17.2 Hz, 1H), 5.36 (d, J¼4.0 Hz, 1H), 5.87–
5.97 (m, 1H), 7.25–7.35 (m, 15H); 13C NMR (CDCl3,
100 MHz): d 170.2, 170.1, 170.0, 169.0, 138.7, 138.1,
138.0, 133.6, 128.4, 128.3, 128.2, 127.9, 127.7, 127.6,
127.4, 118.1, 101.2, 95.3, 81.8, 79.8, 77.6, 75.5, 74.7, 73.0,
71.0, 70.6, 69.8, 68.7, 68.2, 67.9, 66.9, 61.0, 20.6, 20.5,
20.5, 20.4; HR ESI-MS: m/z calcd for C44H52O15
[M+Na]+: 843.3204; found: 843.3173.
4.2.6. 1,2:3,4-Di-O-isopropylidene-6-thio-(20,30,40,60-
tetra-O-acetyl-b-D-galactopyranosyl)-a-D-galactopyr-
anoside (29). Colorless syrup; Rf 0.22 (petroleum ether/
EtOAc, 3:1); [a]D21 ꢀ38.4 (c 2.0, CHCl3); 1H NMR
(CDCl3, 400 MHz): d 1.33, 1.34, 1.45, 1.53 (4ꢃs, each
3H), 1.98, 2.04, 2.06, 2.15 (4ꢃs, each 3H), 2.80 (dd,
J¼6.0, 13.6 Hz, 1H), 2.98 (dd, J¼7.2, 14.0 Hz, 1H), 3.90–
3.94 (m, 2H), 4.11–4.14 (m, 2H), 4.28–4.31 (m, 2H), 4.61
(dd, J¼2.4, 8.0 Hz, 1H), 4.70 (d, J¼10.0 Hz, 1H), 5.05
(dd, J¼3.2, 10.0 Hz, 1H), 5.21 (t, J¼10.0 Hz, 1H), 5.42 (d,
J¼2.4 Hz, 1H), 5.51 (d, J¼4.8 Hz, 1H); 13C NMR (CDCl3,
100 MHz): d 170.1, 170.0, 169.9, 169.4, 109.3, 108.6,
96.4, 84.2, 74.3, 71.8, 71.7, 70.8, 70.3, 69.0, 67.4, 67.2,
61.4, 26.0, 25.9, 24.8, 24.4, 20.6, 20.6, 20.5, 20.5; HR
ESI-MS: m/z calcd for C26H38O14S [M+Na]+: 629.1880;
found: 629.1873.
4.2.3. Allyl 2,3,6-tri-O-benzyl-4-O-(20,30,40,60-tetra-O-
acetyl-b-D-glucopyranosyl)-a-D-glucopyranoside (19).
Colorless syrup; Rf 0.23 (petroleum ether/EtOAc, 3:1);
1
[a]2D1 +6.3 (c 0.7, CHCl3); H NMR (CDCl3, 400 MHz):
d 1.93, 1.94, 1.97, 1.99 (4ꢃs, each 3H), 3.25–3.29 (m, 1H),
3.49 (dd, J¼4.0, 8.8 Hz, 1H), 3.58 (dd, J¼1.6, 10.4 Hz,
1H), 3.68 (d, J¼7.2 Hz, 1H), 3.77 (dd, J¼3.2, 11.2 Hz,
1H), 3.84–3.89 (m, 3H), 4.00 (dd, J¼6.8, 12.8 Hz, 1H),
4.10 (dd, J¼6.4, 17.6 Hz, 1H), 4.09–4.17 (m, 1H), 4.40
(d, J¼12.4 Hz, 1H), 4.50 (d, J¼7.6 Hz, 1H), 4.58 (d,
J¼12.4 Hz, 1H), 4.72 (d, J¼12.0 Hz, 1H), 4.75 (d,
J¼5.2 Hz, 1H), 4.77 (d, J¼3.6 Hz, 1H), 4.78 (d, J¼4.4 Hz,
1H), 4.89 (t, J¼9.2 Hz, 1H), 4.95 (t, J¼9.2 Hz, 1H), 4.98
(d, J¼11.2 Hz, 1H), 5.02 (t, J¼9.6 Hz, 1H), 5.22 (d, J¼
10.4 Hz, 1H), 5.32 (dd, J¼1.6, 17.6 Hz, 1H), 5.88–5.93 (m,
1H), 7.08–7.40 (m, 15H); 13C NMR (CDCl3, 100 MHz):
d 170.4, 170.0, 169.1, 168.8, 139.3, 138.2, 137.6, 133.6,
128.5, 128.2, 128.0, 127.9, 127.6, 127.2, 127.0, 117.9,
100.0, 95.8, 79.8, 79.0, 77.2, 75.0, 73.6, 73.2, 73.2, 71.9,
71.4, 69.9, 68.3, 68.1, 67.6, 61.5, 20.5, 20.5, 20.4, 20.4; HR
ESI-MS: m/z calcd for C44H52O15 [M+Na]+: 843.3204;
found: 843.3200.
4.2.7. Ethyl 2,3,4-tri-O-benzyl-6-O-(20,30,40,60-tetra-O-
acetyl-b-D-glucopyranosyl)-1-thio-a-D-glucopyranoside
(31). Colorless syrup; Rf 0.24 (petroleum ether/EtOAc, 3:1);
1
[a]2D1 +54.0 (c 0.5, CHCl3); H NMR (CDCl3, 400 MHz):
d 1.26 (t, J¼7.6 Hz, 3H), 1.95, 1.99, 2.01, 2.04 (4ꢃs, each
3H), 2.49–2.57 (m, 2H), 3.45 (t, J¼8.8 Hz, 1H), 3.60–3.65
(m, 1H), 3.72 (dd, J¼4.4, 10.8 Hz, 1H), 3.78 (dd, J¼5.2,
9.2 Hz, 1H), 3.83 (dd, J¼9.6, 18.0 Hz, 1H), 4.05 (dd,
J¼1.6, 10.8 Hz, 1H), 4.11 (dd, J¼2.4, 12.0 Hz, 1H), 4.18–
4.25 (m, 2H), 4.44 (d, J¼8.0 Hz, 1H), 4.52 (d, J¼11.2 Hz,
1H), 4.65 (d, J¼12.0 Hz, 1H), 4.73 (t, J¼11.6 Hz, 2H),
4.85 (d, J¼11.2 Hz, 1H), 4.95 (d, J¼10.8 Hz, 1H), 5.04
(dd, J¼8.0, 9.6 Hz, 1H), 5.08 (t, J¼9.6 Hz, 1H), 5.16 (t,
J¼9.2 Hz, 1H), 5.36 (d, J¼5.2 Hz, 1H), 7.24–7.38 (m,