T. Ziegler et al. / Tetrahedron: Asymmetry 9 (1998) 765–780
775
molecular sieves (5 g). After stirring for 1.5 h, the mixture was neutralized with pyridine, filtered,
washed with aq. 2 M HCl and NaHCO3 solution, dried (Na2SO4) and concentrated. Chromatography
(petroleum ether:ethyl acetate=8:1) of the residue afforded first 10a (1.5 g, 13%); [α]2D0=−4 (c=1.2,
CHCl3) 1H NMR (500 MHz): δ=0.07, 0.09 (s, 6H, Si(CH3)2), 0.81 (s, 6H, Si(CH3)2C(CH3)2), 0.84 (d,
6H, Si(CH3)2C(CH3)2CH(CH3)2, J=6.9 Hz), 1.64 (quint, 1H, Si(CH3)2C(CH3)2CH(CH3)2), 3.64 (dd,
1H, 11-Hb, J11b,21=6.9 Hz, J11a,11b=10.6 Hz), 3.70 (dd, 1H, 11-Ha, J11a,21=6.4 Hz), 4.25–4.28 (m, 1H,
21-H), 4.74 (dd, 1H, 42-H, J32,42=5.3 Hz, J42,52=3.5 Hz), 4.76–4.77 (m, 2H, 62-Ha, 62-Hb), 5.32 (d, 1H,
41-Hcis, J31,41cis=10.5 Hz), 5.37–5.41 (m, 2H, 12-H, 41-Htrans), 5.49 (s, 1H, 22-H), 5.63 (d, 1H, 32-H), 5.76
(ddd, 1H, 31-H, J21,31=7.2 Hz, J31,41trans=17.4 Hz), 6.09–6.12 (m, 1H, 52-H), 7.27–8.09 (m, 20H, C6H5);
13C NMR (125 MHz): δ=−3.2, −3.1 (Si(CH3)2), 18.6, 18.7 (Si(CH3)2C(CH3)2CH(CH3)2), 20.3, 20.4
(Si(CH3)2C(CH3)2), 25.3 (Si(CH3)2C(CH3)2), 34.2 (Si(CH3)2C(CH3)2CH(CH3)2), 64.0 (C-62), 65.9 (C-
12), 70.5 (C-52), 77.9 (C-21), 78.0 (C-32), 81.3 (C-22), 82.6 (C-42), 102.9 (C-12, JC12,H12=176.7 Hz),
119.8 (C-41), 134.3 (C-31), 165.6, 165.9, 166.3 (CO); anal. calcd for C46H52O11Si (809.0): C, 68.30; H,
6.48; found: C, 68.55; H, 6.58.
Eluted next was 10b (6.94 g, 60%); [α]2D0=+75 (c=1.0, CHCl3); 1H NMR: (500 MHz)
δ=0.05, 0.11 (2 s, 6H, Si(CH3)2), 0.79, 0.80 (2 s, 6H, Si(CH3)2C(CH3)2), 0.83, 0.84 (2 d, 6H,
Si(CH3)2C(CH3)2CH(CH3)2, J=6.8 Hz), 1.57 (quint, 1H, Si(CH3)2C(CH3)2CH(CH3)2), 3.61 (dd, 1H,
11-Hb, J11b,21=5.5 Hz, J11a,11b=10.7 Hz), 3.73 (dd, 1H, 11-Ha, J11a,21=5.7 Hz), 4.27–4.34 (m, 1H, 21-H,
52-H), 4.42 (dd, 1H, 62-Hb, J52,62b=6.7 Hz, J62a,62b=11.3 Hz), 4.68 (dd, 1H, 62-Ha, J52,62a=6.5 Hz),
4.92 (d, 1H, 12-H, J12,22=8.1 Hz), 5.20–5.28 (m, 2H, 41-Hcis, 41-Htrans), 5.57 (dd, 1H, 32-H, J22,32=10.4
Hz, J32,42=3.4 Hz), 5.63 (ddd, 1H, 31-H, J21,31=7.2 Hz, J31,41cis=10.3 Hz, J31,41trans=17.4 Hz), 5.83
(dd, 1H, 22-H), 5.99 (d, 1H, 42-H), 7.22–8.11 (m, 20H, C6H5); 13C NMR (125 MHz): δ=−3.5, −3.2
(Si(CH3)2), 18.5 (Si(CH3)2C(CH3)2CH(CH3)2), 20.3 (Si(CH3)2C(CH3)2), 25.0 (Si(CH3)2C(CH3)2),
34.2 (Si(CH3)2C(CH3)2CH(CH3)2), 62.0 (C-62), 65.5 (C-11), 68.1 (C-42), 69.8 (C-22), 71.1 (C-52), 72.0
(C-32), 80.0 (C-21), 98.5 (C-12), 119.2 (C-41), 134.9 (C-31), 165.1, 165.6, 166.0 (4×CO); anal. calcd
for C46H52O11Si (809.0): C, 68.30; H, 6.48; found: C, 68.28; H, 6.51.
3.18. (R)-1-Hydroxy-3-butene-2-yl 2,3,4,6-tetra-O-benzoyl-β-D-galactopyranoside 11
Aqueous 40% HF (1.5 ml) was added to a solution of 10b (5.52 g, 6.82 mmol) in 50 ml MeCN. The
mixture was kept at room temperature for 2 h, diluted with CH2Cl2, washed with water and aq. NaHCO3
solution, dried (Na2SO4) and concentrated. The residue was crystallized from hexane–acetone to afford
11 (3.75 g, 82%); mp: 153–154°C; [α]2D0=+110 (c=1.4, CHCl3); 1H NMR (500 MHz): δ=2.64 (dd, 1H,
OH), 3.59 (ddd, 1H, 11-Hb, J11b,OH=4.4 Hz, J11b,21=7.4 Hz, J11a,11b=11.9 Hz), 3.64 (ddd, 1H, 11-Ha,
J
J
11a,OH=9.1 Hz, J11a,21=3.1 Hz), 4.33–4.37 (m, 2H, 21-H, 52-H), 4.50 (dd, 1H, 62-Hb, J52,62b=5.9 Hz,
62a,62b=11.5 Hz), 4.63 (dd, 1H, 62-Ha, J52,62a=7.0 Hz), 4.91 (d, 1H, 12-H, J12,22=8.1 Hz), 5.13 (d, 1H,
41-Hcis, J31,41cis=10.4 Hz), 5.25 (d, 1H, 41-Htrans, J31,41trans=17.3 Hz), 5.57–5.62 (m, 1H, 31-H), 5.62 (dd,
1H, 32-H, J22,32=10.4 Hz, J32,42=3.6 Hz), 5.85 (dd, 1H, 22-H), 6.01 (d, 1H, 42-H), 7.23–8.11 (m, 20H,
4×C6H5); 13C NMR (125 MHz): δ=62.6 (C-62), 65.7 (C-11), 68.5 (C-42), 70.2 (C-22), 72.0 (C-32, 52),
83.1 (C-21), 100.4 (C-12), 119.5 (C-41), 134.1 (C-31), 165.7, 165.9, 166.0, 166.5 (4×CO); anal. calcd
for C38H34O11 (666.7): C, 68.46; H, 5.14; found: C, 68.38; H, 5.20.
3.19. (R)-1-p-Toluenesulfonyloxy-3-butene-2-yl 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside 13
A suspension of (R)-5d (3.00 g, 12.40 mmol), AgOTf (3.53 g, 13.60 mmol) and molecular sieves
3 Å in CH2Cl2 (130 ml) was stirred at room temperature for 30 min in the dark. The mixture was