7430
G.R. Morais et al. / Tetrahedron 64 (2008) 7426–7431
J4,5 9.9 Hz), 5.34 (dd, 1H, H-3, J2,3 9.9 Hz, J3,4 9.9 Hz), 5.58 (dd, 1H, H-
2, J1,2 9.9 Hz, J2,3 9.9 Hz), 7.33–7.36 (m, 5H); dC (150 MHz, CDCl3)
20.63 (2C), 20.65, 20.70, 53.01, 55.06, 58.53, 61.30, 65.58, 65.99.
67.50, 73.43, 87.62, 125.78 (2C), 128.83 (2C), 129.11, 169.27, 169.28,
169.34, 170.20.
2.16 (4s, 12H, 4OAc), 3.14 (q, 2H, J 7.4 Hz), 4.04 (dd, 1H, H-5, J5,6a
6.0 Hz, J5,6b 6.8 Hz), 4.11 (dd, 1H, H-6a, J5,6a 6.0 Hz, J6a,6b 11.5 Hz),
4.18 (dd, 1H, H-6b, J5,6b 6.8 Hz, J6a,6b 11.5 Hz), 4.41 (d, 1H, H-1, J1,2
9.9 Hz), 5.12 (dd, 1H, H-3, J3,4 3.2 Hz, J2,3 9.9 Hz), 5.45 (dd, 1H, H-4,
J4,5 1.0 Hz, J3,4 3.2 Hz), 5.66 (dd, 1H, H-2, J1,2 9.9 Hz, J2,3 9.9 Hz); dC
(150 MHz, CDCl3) 5.48, 20.62, 20.71, 20.72, 20.84, 43.84, 61.19,
63.54, 66.76, 71.33, 75.62, 88.25, 169.55, 170.04, 170.06, 170.36; MS
(ESI) m/z: 447.1 [MþNa]; HRMS (ESI, MþNH4) calcd for
Minor diastereoisomer: Rf¼0.31 (EtOAc–petroleum ether 1:1);
dH (600 MHz, CDCl3) 2.01, 2.01, 2.03, 2.05 (4s, 12H, 4OAc), 3.43–3.47
2
(m, 2H), 3.53 (dd, 1H, 3J 3.1 Hz, J 14.4 Hz), 3.85–3.87 (m, 1H, H-5),
3.90 (d, 1H, 3J 1.7 Hz), 4.16 (dd, 1H, H-6a, J5,6a 4.8 Hz, J6a,6b 12.7 Hz),
4.25 (dd, 1H, H-6b, J5,6b 2.2 Hz, J6a,6b 12.7 Hz), 4.52 (d, 1H, H-1, J1,2
9.9 Hz), 5.11 (dd, 1H, H-4, J3,4 9.9 Hz, J4,5 9.9 Hz), 5.29 (dd, 1H, H-3,
J2,3 9.9 Hz, J3,4 9.9 Hz), 5.61 (dd,1H, H-2, J1,2 9.9 Hz, J2,3 9.9 Hz), 7.25–
7.28 (m, 5H); dC (150 MHz, CDCl3) 20.61, 20.68, 20.72, 20.83, 53.30,
54.50, 58.09, 61.49, 65.62, 66.31, 67.38, 73.17, 88.53, 125.78 (2C),
128.85 (2C), 129.01, 168.43, 169.23, 170.59, 171.67; MS (ESI) m/z:
C16H28NO11S 442.1378, found 442.1381.
4.4.9. Methyl 2,3,4,6-tetra-O-acetyl-1-sulfonyl-b-D-
galactopyranoside (2k)
20
Oil, [
a
]
þ14ꢂ0.5 (c 0.63, CHCl3); Rf¼0.30 (EtOAc–petroleum
D
ether 1:1); dH (600 MHz, CDCl3) 1.99, 2.04, 2.07, 2.17 (4s,12H, 4OAc),
2.06 (s, 3H, CH3), 4.08 (dd, 1H, H-5, J5,6a 6.1 Hz, J5,6b 6.5 Hz), 4.13 (dd,
1H, H-6a, J5,6a 6.1 Hz, J6a,6b 11.5 Hz), 4.20 (dd, 1H, H-6b, J5,6b 6.5 Hz,
J6a,6b 11.5 Hz), 4.31 (d, 1H, H-1, J1,2 9.9 Hz), 5.12 (dd, 1H, H-3, J3,4
2.9 Hz, J2,3 9.9 Hz), 5.45 (d, 1H, H-4, J3,4 2.9 Hz), 5.59 (dd, 1H, H-2, J1,2
9.9 Hz, J2,3 9.9 Hz); dC (150 MHz, CDCl3) 20.60, 20.72 (2C), 20.83,
36.30, 61.06, 63.79, 66.78, 71.19, 75.62, 88.97, 169.80, 169.99, 170.02,
170.39; MS (ESI) m/z: 433.2 [MþNa]; HRMS (ESI, MþNH4) calcd for
567.2 [MþNa]; HRMS (ESI, MþNH4) calcd for C23H32NO12
S
546.1640, found 546.1637.
4.4.5. Benzyl 2,3,4,6-tetra-O-acetyl-1-sulfonyl-a-D-
mannopyranoside (2g)
20
Colourless solid, mp: 174–176 ꢀC; [
a
]
þ83.5ꢂ1 (c 0.46, CHCl3);
D
Rf¼0.36 (EtOAc–petroleum ether 1:1); nmax (KBr) 3062, 3025, 2960,
C15H26NO11S 428.1221, found 428.1218.
1758, 1312, 1246, 1167, 1112, 978, 540 cmꢁ1
;
dH (600 MHz, CDCl3)
1.97, 2.05, 2.09, 2.12 (4s, 12H, 4OAc), 4.13 (dd, 1H, H-6a, J5,6a 1.5 Hz,
J6a,6b 12.5 Hz), 4.24 (d,1H, 2J 14.4 Hz), 4.27 (dd,1H, H-6b, J5,6b 6.0 Hz,
J6a,6b 12.5 Hz), 4.51 (d, 1H, 2J 14.4 Hz), 4.66 (d, 1H, H-1, J1,2 1.7 Hz),
4.70–4.72 (m, 1H, H-5), 5.27 (dd, 1H, H-4, J3,4 9.9 Hz, J4,5 9.9 Hz),
5.57 (dd,1H, H-3, J2,3 3.7 Hz, J3,4 9.9 Hz), 5.88 (dd,1H, H-2, J1,2 1.7 Hz,
J2,3 3.7 Hz), 7.40–7.41 (m, 5H); dC (150 MHz, CDCl3) 20.58, 20.74,
20.75, 20.86, 57.13, 62.63, 64.55, 65.33, 68.93, 73.45, 86.13, 126.92,
129.31 (2C), 129.45, 130.92 (2C), 169.20, 169.32, 169.75, 170.49; MS
4.4.10. (30-Cyanopropyl) 2,3,4,6-tetra-O-acetyl-1-sulfonyl-
b-D-
galactopyranoside (2l)
20
Oil, [
a
]
D
þ3ꢂ1 (c 0.90, CHCl3); Rf¼0.13 (EtOAc–petroleum ether
1:1); nmax (film) 3018, 2946, 2880, 2268, 1627, 1397, 1452, 1306,
1125, 1098 cmꢁ1
;
dH (600 MHz, CDCl3) 1.99, 2.05, 2.06, 2.18 (4s, 12H,
4OAc), 2.23–2.37 (m, 2H, CH2), 2.57–2.66 (m, 2H, S(O2)CH2), 3.29 (t,
2H, CH2CN, 3J 7.2 Hz), 4.07 (dd,1H, H-5, J5,6a 6.0 Hz, J5,6b 6.7 Hz), 4.13
(dd, 1H, H-6a, J5,6a 6.0 Hz, J6a,6b 11.7 Hz), 4.21 (dd, 1H, H-6b, J5,6b
6.7 Hz, J6a,6b 11.7 Hz), 4.41 (d, 1H, H-1, J1,2 9.9 Hz), 5.12 (dd, 1H, H-3,
J3,4 3.4 Hz, J2,3 9.9 Hz), 5.46 (d,1H, H-4, J3,4 3.4 Hz), 5.63 (dd,1H, H-2,
J1,2 9.9 Hz, J2,3 9.9 Hz); dC (150 MHz, CDCl3) 16.51, 17.83, 20.60, 20.74
(2C), 20.80, 47.33, 61.18, 63.50, 66.73, 71.13, 75.89, 89.18, 118.16,
169.62, 169.98, 170.06, 170.40; MS (ESI) m/z: 486 [MþNa]; HRMS
(ESI, MþNH4) calcd for C18H29N2O11S 481.1487, found 481.1486.
(ESI) m/z: 509 [MþNa]; HRMS (ESI, MþNH4) calcd for C21H30NO11
S
504.1534, found 504.1525.
4.4.6. (Benzyl)-6-deoxy-2,3,4-tri-O-acetyl-1-sulfonyl-a-L-
rhamnopyranose (2h)
20
Colourless solid, mp: 72–73 ꢀC; [
a
]
ꢁ82ꢂ0.5 (c 0.75, CHCl3);
D
Rf¼0.71 (EtOAc–petroleum ether 1:1); dH (600 MHz, CDCl3) 1.27 (d,
3H, 3J 6.1 Hz), 1.97, 2.05, 2.08 (3s, 9H, 3OAc), 4.22 (d, 1H, 2J 14.4 Hz),
4.48 (d, 1H, 2J 14.4 Hz), 4.53–4.58 (m, 1H, H-5), 4.62 (d, 1H, H-1, J1,2
1.6 Hz), 5.07 (dd, 1H, H-4, J3,4 9.4 Hz, J4,5 9.4 Hz), 5.52 (dd, 1H, H-3,
J2,3 3.6 Hz, J3,4 9.4 Hz), 5.87 (dd, 1H, H-2, J1,2 1.6 Hz, J2,3 3.6 Hz), 7.39–
7.40 (m, 5H); dC (150 MHz, CDCl3) 18.12, 20.63, 20.76, 20.85, 57.24,
64.91, 68.97, 70.08, 71.74, 86.46, 127.10, 128.23 (2C), 129.34, 130.92
(2C), 169.30, 169.41, 170.01; MS (ESI) m/z: 446.2 [MþNH4]; HRMS
(ESI, MþNH4) calcd for C19H28NO9S 446.1479, found 446.1471.
4.4.11. (20-Oxo-20-phenylethyl)-2,3,4,6-tetra-O-acetyl-1-sulfonyl-
b-D-galactopyranoside (2m)
20
Oil, [
a
]
ꢁ6.0ꢂ0.5 (c 0.6, CHCl3); Rf¼0.42 (EtOAc–petroleum
D
ether 2:1); dH (600 MHz, CDCl3) 1.77, 1.99, 2.05, 2.17 (4s, 12H, 4OAc),
4.02–4.16 (m, 3H, H-5, H-6a and H-6b), 4.68 (d, 1H, 2J 15.4 Hz), 4.83
(d, 1H, 2J 15.4 Hz), 4.94 (d, 1H, H-1, J1,2 9.9 Hz), 5.15 (dd, 1H, H-3, J3,4
3.3 Hz, J2,3 9.9 Hz), 5.45 (d, 1H, H-4, J3,4 3.3 Hz), 5.82 (dd, 1H, H-2, J1,2
9.9 Hz, J2,3 9.9 Hz), 7.52 (t, 2H, 3J 7.5 Hz), 7.56 (t, 1H, 3J 7.5 Hz), 7.94
(d, 2H, 3J 7.5 Hz); dC (150 MHz, CDCl3) 20.37, 20.63, 20.74, 20.79,
56.82, 61.49, 63.04, 66.96, 71.46, 76.08, 88.17, 128.92 (2C), 129.20
(2C), 134.88, 135.52, 169.19, 170.05, 170.23, 170.33, 188.45; MS (ESI)
4.4.7. Hexanyl 2,3,4,6-tetra-O-acetyl-1-sulfonyl-b-D-
galactopyranoside (2i)
20
Oil, [
a]
ꢁ3.0ꢂ0.5 (c 0.47, CHCl3); Rf¼0.46 (EtOAc–petroleum
m/z: 537 [MþNa]; HRMS (ESI, MþNH4) calcd for C22H30NO12
S
D
ether 1:1); dH (600 MHz, CDCl3) 0.88 (t, 3H, 3J 6.9 Hz), 1.31–1.32 (m,
4H), 1.41–1.45 (m, 2H), 1.82–1.85 (m, 2H), 1.99, 2.04, 2.06, 2.17 (4s,
12H, 4OAc), 3.09–3.11 (m, 2H), 4.04 (dd, 1H, H-5, J5,6a 6.1 Hz, J5,6b
6.8 Hz), 4.13 (dd,1H, H-6a, J5,6a 6.1 Hz, J6a,6b 11.5 Hz), 4.17 (dd,1H, H-
6b, J5,6b 6.8 Hz, J6a,6b 11.5 Hz), 4.38 (d, 1H, H-1, J1,2 9.8 Hz), 5.12 (dd,
1H, H-3, J3,4 2.8 Hz, J2,3 9.9 Hz), 5.45 (d,1H, H-4, J3,4 2.8 Hz), 5.66 (dd,
1H, H-2, J1,2 9.8 Hz, J2,3 9.9 Hz); dC (150 MHz, CDCl3) 14.03, 20.62,
20.70, 20.74, 20.80, 20.84, 22.39, 28.35, 31.30, 49.17, 61.20, 63.52,
66.75, 71.33, 75.59, 88.47, 170.05 (2C), 170.07, 170.35; MS (ESI) m/z:
503 [MþNa]; HRMS (ESI, MþNa) calcd for C20H32O11NaS 503.1558,
found 503.1563.
532.1483, found 532.1483.
4.4.12. Pyrimidinyl 2,3,4,6-tetra-O-acetyl-1-sulfonyl-b-D-
galactopyranoside (2n)
20
Oil, [
a
]
ꢁ19ꢂ0.5 (c 0.7, CHCl3); Rf¼0.12 (EtOAc–petroleum
D
ether 2:1); nmax (film) 3019, 2916, 2848, 1700, 1390, 1255 cmꢁ1
; dH
(600 MHz, CDCl3) 1.89, 2.00, 2.08, 2.13 (4s, 12H, 4OAc), 3.84 (dd, 1H,
H-6a, J5,6a 6.3 Hz, J6a,6b 11.4 Hz), 3.90 (dd, 1H, H-5, J5,6b 4.9 Hz, J5,6a
6.3 Hz), 3.93 (dd, 1H, H-6b, J5,6b 4.9 Hz, J6a,6b 11.4 Hz), 5.14 (dd, 1H,
H-3, J3,4 3.4 Hz, J2,3 9.9 Hz), 5.23 (d, 1H, H-1, J1,2 9.9 Hz), 5.40 (d, 1H,
H-4, J3,4 3.4 Hz), 6.00 (dd, 1H, H-2, J1,2 9.9 Hz, J2,3 9.9 Hz), 7.59 (t, 1H,
3J 4.8 Hz), 8.98 (d, 2H, 3J 4.8 Hz); dC (150 MHz, CDCl3) 20.58, 20.65,
20.71, 20.82, 60.91, 63.50, 66.61, 71.58, 75.30, 86.94, 124.00, 158.71
(2C), 164.28, 169.05, 170.05, 170.17 (2C); MS (ESI) m/z: 497.0
[MþNa]; HRMS (ESI, MþNH4) calcd for C18H26N3O11S 492.1283,
found 492.1284.
4.4.8. Ethyl 2,3,4,6-tetra-O-acetyl-1-sulfonyl-b-D-
galactopyranoside (2j)
20
Oil, [
a
]
þ7ꢂ0.5 (c 0.57, CHCl3); Rf¼0.24 (EtOAc–petroleum
D
ether 1:1); dH (600 MHz, CDCl3) 1.39 (t, 3H, J 7.4 Hz),1.99, 2.04, 2.06,