JOURNAL OF CARBOHYDRATE CHEMISTRY
21
1
3
-
1
1
1
1
1
SCH(CH ) ), 0.72 (3 H, d, J¼ 6.0 Hz, H-6’). C NMR (100 MHz, CDCl ) d
3
2
3
66.0, 165.9, 165.4, 165.3, 164.9 (C ¼ O), 139.3, 138.9, 138.6, 137.0, 135.6, 133.8,
33.5, 133.3, 133.2, 133.2, 133.2, 130.4, 130.1, 130.1, 130.1, 130.1, 130.0, 130.0,
29.9, 129.9, 129.9, 129.9, 129.8, 129.6, 129.5, 129.1, 129.0, 128.9, 128.9, 128.6,
28.6, 128.5, 128.5, 128.5, 128.5, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3, 128.2,
28.2, 127.9, 127.6, 127.6, 127.6, 127.5, 127.5, 127.4, 127.2, 126.5, 126.5, 126.5
(
Ar), 101.9 (PhCHO ), 101.6, 99.8 (C-1’), 83.7, 80.5, 79.5, 79.4, 78.3, 76.1, 74.7,
2
7
3.2, 72.7, 72.1, 71.9, 71.7, 70.9, 70.0, 68.7, 68.3, 63.1, 39.0 (-SCH(CH ) ), 33.0,
3
2
2
3.2 (-SCH(CH ) ), 23.1 (-SCH(CH ) ), 17.3 (C-6’). HRMS calc. for
3 2 3 2
þ
C H NaO S [M þ Na] : 1479.4627, found: 1479.4614.
8
4
80
19 2
Compound 29
A solution of 19 (43.3 mg, 0.06 mmol), 23 (40 mg, 0.05 mmol) and DTBMP
(
19.0 mg, 0.09 mmol) in CH Cl (0.91 mL) in the presence of 4 Å MS
2 2
ꢂ
(100 wt%) was stirred at 0 C for 10min, Tf O (9.4lL, 0.06 mmol) was added,
2
ꢂ
the solution was stirred at 0 C for 30 min. The reaction mixture was quenched
with Et N, then filtered and extracted with EtOAc. The organic phase was
3
washed with brine, dried (Na SO ), concentrated, and purified by silica gel col-
2
4
umn chromatography to give compound 29 (45.8 mg, 69% yield) as white solid,
1
R ¼ 0.51 (petroleum-EtOAc 3:1). H NMR (400 MHz, CDCl ) d 8.05–8.01
f
3
(
4 H, m, Ar-H), 7.92 (2 H, d, J¼ 7.2 Hz, Ar-H), 7.82 (2 H, dd, J¼ 8.0, 0.8 Hz,
Ar-H), 7.62–7.56 (2 H, m, Ar-H), 7.50–7.11 (32H, m, Ar-H), 6.70 (2H, m, Ar-
0
0
H), 5.63 (1H, d, J¼ 5.2 Hz, H-1 ), 5.50 (1 H, dd, J¼ 3.2, 0.8 Hz), 5.47 (1 H, s,
PhCHO ), 5.41 (1 H, d, J¼ 8.0 Hz), 5.25 (1 H, dd, J¼ 10.0, 9.2 Hz, H-2), 5.01
2
(
1 H, d, J¼ 1.6 Hz, H-1’), 4.82 (1 H, d, J¼ 11.2 Hz, ArCH ), 4.69 (1 H, m), 4.46
2
(
1 H, d, J¼ 10.0 Hz, H-1), 4.47–4.43 (2 H, m), 4.34 (1 H, dd, J¼ 10.4, 4.8 Hz),
4
.17 (1 H, d, J¼ 13.2 Hz, ArCH ), 4.12 (1 H, dd, J¼ 8.8, 3.6 Hz), 4.08 (1 H, d,
2
J¼ 12.4 Hz, ArCH ), 3.96–3.92 (2 H, m), 3.90 (1 H, dd, J¼ 9.6, 6.4 Hz), 3.83
2
(
1 H, d, J¼ 12.0 Hz, ArCH ), 3.73 (1 H, dd, J¼ 10.4, 10.0 Hz), 3.66–3.61 (2 H,
2
m), 3.58 (1H, t, J¼ 9.2Hz), 3.46 (1H, td, J¼ 9.6, 4.8 Hz), 3.38 (1 H, t,
J¼ 9.6 Hz), 3.21 (1 H, hepta., J¼ 6.4 Hz, -SCH(CH ) ), 1.16 (3 H, d, J¼ 6.4 Hz,
3
2
-
SCH(CH ) ), 1.12 (3 H, d, J¼ 6.4 Hz, -SCH(CH ) ), 0.77 (3 H, d, J¼ 6.0 Hz,
3
2
3 2
13
H-6’). C NMR (100 MHz, CDCl ) d 166.2, 165.3, 165.0, 164.5 (C ¼ O), 139.2,
3
1
1
1
1
38.9, 138.8, 137.0, 135.5, 134.5, 133.7, 133.6, 133.4, 133.2, 133.1, 130.4, 130.4,
30.3, 130.3, 130.1, 130.1, 129.9, 129.9, 129.8, 129.8, 129.7, 129.6, 129.5, 129.2,
29.1, 129.1, 128.8, 128.8, 128.6, 128.6, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3,
28.3, 128.2, 128.2, 128.1, 128.1, 128.1, 127.9, 127.9, 127.9, 127.5, 127.2, 127.1,
27.1, 127.1, 126.7, 126.5, 126.5 (Ar), 121.7 (PhCO ), 102.0 (PhCHO ), 99.5 (C-
1
1
3
2
0
0
’), 97.4 (C-1 ), 83.9 (C-1), 80.1, 79.6, 78.2, 77.9, 75.2, 72.9, 72.2, 71.2, 71.0,
7
0.0, 68.8, 68.6, 68.2, 67.8, 67.6, 63.8, 38.9 (-SCH(CH ) ), 33.0, 23.2
3
2
(
-SCH(CH ) ), 23.1 (-SCH(CH ) ), 17.5 (C-6’). HRMS calc. for C H NaO S
3 2 3 2 84 80 19 2
þ
[M þ Na] : 1479.4627, found: 1479.4612.