Molecules 2005, 10
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1), 5.17 (dd, 1H, J = 9.1, 3.1 Hz, H-3), 5.35 (dd, 1H, J = 9.1, 8.8 Hz, H-4), 6.20 (dd, 1H, J = 3.1, 2.9
Hz, H-2), 7.35-7.55 (m, 5H, Harom); 13C-NMR (CDCl3) δ 21.1 (2xMe), 21.2 (Me), 21.4 (Me), 62.8 (C-
6), 67.2 (C-4), 69.6 (C-2), 70.1 (C-3), 71.5 (C-5), 76.2 (C-1), 126.8, 128.9, 129.5 and 135.6 (Carom),
170.0 (CO), 170.3 (CO), 170.7 (CO), 171.1 (CO). All the data are in agreement with the literature [21].
(4,6-Di-O-tert-butyldimethylsilyl-β-D-mannopyranosyl)benzene (13) (as a mixture with 14). Yield
1
56%, oil, Rf 0.45 (petroleum ether-ethyl acetate 4:1); H-NMR (CDCl3) δ 0.10 (s, 3H, SiMe), 0.14 (s,
3H, SiMe), 0.15 (s, 3H, SiMe), 0.19 (s, 3H, SiMe), 0.93 (s, 9H, CMe3), 0.94 (s, 9H, CMe3), 1.70 (bs,
1H, OH), 2.40 (bs, 1H, OH), 3.31 (ddd, 1H, J = 9.2, 5.5, 2.9 Hz, H-5), 3.66 (dd, 1H, J = 8.8, 3.3 Hz,
H-3), 3.88 (dd, 1H, J = 9.2, 8.8 Hz, H-4), 3.93 (m, 2H, H-6), 4.06 (d, 1H, J = 3.3 Hz, H-2), 4.60 (s, 1H,
13
H-1), 7.28 (m, 5H, Harom); C-NMR (CDCl3) δ -5.1 (CH3), -5.0 (CH3), -4.8 (CH3), -4.0 (CH3), 18.4
(CMe3), 18.5 (CMe3), 26.0 (CMe3), 26.1 (CMe3), 62.3 (C-6), 69.1, 73.1, and 76.3 (C-1, C-4, C-5), 79.4
and 81.5 (C-2, C-3), 126.0, 127.7, 128.4 and 138.0 (Carom); Anal. calcd for C24H44O5Si2 (mixture 13 +
14): C, 61.50; H, 9.47. Found: C, 61.86; H, 9.31.
(4,6-Di-O-tert-butyldimethylsilyl-β-D-allopyranosyl)benzene (14) (as a mixture with 13). Yield 14%,
1
oil, Rf 0.45 (petroleum ether-ethyl acetate 4:1); H-NMR (CDCl3) δ 0.00 (s, 3H, SiMe), 0.03 (s, 3H,
SiMe), 0.07 (s, 3H, SiMe), 0.16 (s, 3H, SiMe), 0.90 (s, 9H, CMe3), 0.93 (s, 9H, CMe3), 1.50 (bs, 1H,
OH), 2.60 (bs, 1H, OH), 3.50 (dd, 1H, J = 9.9, 2.9 Hz, H-2), 3.61 (ddd, 1H, J = 9.5, 2.9, 1.5 Hz, H-5),
3.80 (dd, 1H, J = 11.4, 2.9 Hz, H-6), 3.87 (dd, 1H, J = 11.4, 1.5 Hz, H-6), 4.01 (dd, 1H, J = 9.5, 2.9 Hz,
H-4), 4.20 (dd, 1H, J = 2.9, 2.9 Hz, H-3), 4.50 (d, 1H, J = 9.9 Hz, H-1), 7.40 (m, 5H, Harom); 13C-NMR
(CDCl3) δ -5.2 (CH3), -5.0 (CH3), -4.8 (CH3), -4.5 (CH3), 18.0 (CMe3), 18.2 (CMe3), 25.8 (CMe3), 26.0
(CMe3), 62.2 (C-6), 67.8, 71.5 and 73.1 (C-1, C-4, C-5), 76.1 and 77.6 (C-2, C-3), 127.4, 128.0, 128.2
and 137.0 (Carom).
(2,3,4,6-Tetra-O-acetyl-β-D-mannopyranosyl)benzene (15) (as a mixture with 16). Yield 19%, oil, Rf
1
0.30 (petroleum ether-ethyl acetate 1:1); H-NMR (CDCl3) δ 2.00 (s, 3H, Me), 2.03 (s, 3H, Me), 2.11
(s, 3H, Me), 2.20 (s, 3H, Me), 3.83 (ddd, 1H, J = 9.5, 5.9, 2.6 Hz, H-5), 4.21-4.30 (m, 1H, H-6), 4.35
(dd, 1H, J = 12.5, 5.9 Hz, H-6), 4.79 (d, 1H, J = 1.1 Hz, H-1), 5.25 (dd, 1H, J = 10.2, 3.3 Hz, H-3),
5.33 (dd, 1H, J = 10.2, 9.5 Hz, H-4), 5.55 (dd, 1H, J = 3.3, 1.1 Hz, H-2), 7.30 (m, 5H, Harom);
13C-NMR (CDCl3) δ 20.2 (Me), 20.3 (Me), 20.8 (Me), 21.0 (Me), 60.4 (C-6), 66.6 (C-4), 73.1 (C-2),
77.3 (C-3), 77.4 (C-5), 81.8 (C-1), 127.2, 128.7, 129.2, and 136.3 (Carom), 168.7 (CO), 168.9 (CO),
169.2 (CO), 170.6 (CO). All data are in agreement with the literature [21].
(2,3,4,6-Tetra-O-acetyl-β-D-allopyranosyl)benzene (16) (as a mixture with 15). Yield 56%, oil, Rf
1
0.30 (petroleum ether-ethyl acetate 1:1); H-NMR (CDCl3) δ 1.80 (s, 3H, Me), 2.03 (s, 3H, Me), 2.08
(s, 3H, Me), 2.23 (s, 3H, Me), 4.15-4.27 (m, 3H, H-5, H-6), 4.71 (d, 1H, J = 10.3 Hz, H-1), 5.03 (dd,
1H, J = 10.3, 2.9 Hz, H-2), 5.12 (dd, 1H, J = 9.9, 2.6 Hz, H-4), 5.73 (dd, 1H, J = 2.9, 2.6 Hz, H-3),
7.35-7.43 (m, 5H, Harom); 13C-NMR (CDCl3) δ 20.4 (Me), 20.6 (Me), 20.8 (Me), 21.4 (Me), 62.8 (C-6),
66.6 (C-4), 68.5 (C-2), 70.6 (C-3), 71.4 (C-5), 76.2 (C-1), 126.9, 127.2, 128.4 and 136.9 (Carom), 168.8
(CO), 169.2 (CO), 170.0 (CO), 170.8 (CO).