accord with those reported in the literature. The properties of
rearrangement products that have not been reported previously,
or are inadequately described in the literature, are given below.
and 7.6, H-1A), 3.92 (1 H, dd, J 12.5 and 2.2, H-5A), 4.17 (1 H,
dd, J 12.5 and 4.3, H-5B), 4.33 (1 H, dd, J 11.8 and 4.1 H-1B),
5.65–5.75 (3 H, complex, H-2, -3 and -4), 7.30–7.65 (9 H, com-
plex, Ph), 7.94 (2 H, m, Ph), 8.01 (2 H, m, Ph), 8.06 (2 H, m,
Ph); δC 67.4, 67.6, 68.3, 68.9, 70.7, 128.4, 128.4(6), 128.4(7),
129.2, 129.5, 129.7(1), 129.7(8) (2 C), 129.8(3), 133.3(5),
133.3(6), 133.4(1), 165.4(7), 165.5(2), 165.6 (Found: C, 70.0; H,
4.8. C27H22O7 requires C, 70.0; H, 5.0%).
Methyl 2,3-di-O-acetyl-4-O-p-methoxybenzoyl-6-deoxy-ꢀ-D-
glucopyranoside 18
Oil, [α]1D8 ϩ33.2 (c 1.7, CHCl3); δH 1.23 (3 H, d, J 6.3, Me-5),
1.88 (3 H, s, Ac), 2.08 (3 H, s, Ac), 3.42 (3 H, s, OMe), 3.85 (3 H,
s, OMe), 4.00 (1 H, dq, J 9.8 and 6.3, H-5), 4.92–4.94 (2 H, m,
H-1 and H-2), 5.00 (1 H, t, J 9.7, H-4), 5.62 (1 H, [t], J 9.6, H-3),
6.91 (2 H, m, Ph), 7.93 (2 H, m, Ph); δC 17.3, 20.5, 20.8, 55.3,
55.4, 65.3, 69.7, 71.4, 74.2, 96.7, 128.5, 129.8, 133.5, 163.7,
165.1, 169.9, 170.1 (Found: C, 57.5; H, 6.0. C19H24O9 requires
C, 57.6; H, 6.1%).
Tri-O-benzoyl-2-deoxy-ꢁ-L-threo-pentopyranose 35
Mp 160–161 ЊC (from diethyl ether–hexane), [α]2D2 ϩ193.1 (c 1.7,
CHCl3). The -enantiomer46 shows mp 159–161 ЊC, [α]2D2 Ϫ195
(c 1.0, CHCl3). Compound 35 shows δH 2.36 (1 H, ddd, J 13.2,
5.0 and 1.8, H-2A), 2.65 (1 H, ddd, J 13.2, 11.8 and 2.6, H-2B),
4.16 (1 H, dd, J 13.2,and 3.0, H-5A), 4.32 (1 H, dd, J 13.2 and
1.4, H-5B), 5.68 (1 H, dd, J 3.0, and 1.4, H-4), 5.82 (1 H, ddd,
J 11.8, 5.0 and 3.0, H-3), 6.66 (1 H, dd, J 2.6 and 1.8, H-1),
7.30–7.65 (9 H, complex, Ph), 7.94 (2 H, m, Ph), 8.12 (4 H, m,
Ph); δC 30.3, 63.4, 66.3, 68.0, 92.5, 128.4, 128.5, 128.6, 129.4(8),
129.5(2), 129.7, 129.8 (2 C), 129.9, 133.3, 133.4, 133.6, 164.8,
165.6, 165.8 (Found: C, 69.8; H, 4.9. C27H22O7 requires C,
70.0; H, 5.0%).
Methyl 2,3-di-O-acetyl-6-O-p-methoxybenzoyl-4-deoxy-ꢀ-D-
xylo-hexopyranoside 19
Mp 86–87 ЊC (from CH2Cl2–hexane); [α]2D2 ϩ190.2 (c 1.1,
CHCl3); δH 1.67 (1 H, [q], J 12.0, H-4A), 2.02 (3 H, s, OMe),
2.09 (3 H, s, OMe), 2.25 (1 H, ddd, J 12.0, 5.3 and 2.2, H-4B),
3.37 (3 H, s, OMe), 3.86 (3 H, s, OMe), 4.20 (1 H, m, H-5), 4.32
(1 H, dd, J 11.7 and 3.9, H-6A), 4.34 (1 H, dd, J 11.7 and 5.8,
H-6B), 4.89 (1 H, dd, J 10.2 and 3.6, H-2), 4.95 (1 H, d, J 3.6,
H-1), 5.32 (1 H, ddd, J 12.0, 10.2 and 5.3, H-3), 7.91 (2 H, m,
Ph), 7.97 (2 H, m, Ph); δC 20.9, 21.0, 32.9, 55.1, 55.4, 65.2, 65.6,
67.6, 71.8, 97.5, 113.7, 122.1, 131.7, 163.5, 165.9, 170.1, 170.5
(Found: C, 57.5; H, 6.1. C19H24O9 requires C, 57.6; H, 6.1%).
1,5-Anhydro-tri-O-benzoyl-L-rhamnitol 3847
Mp 165–168 ЊC (from diethyl ether) (lit.47 169–170 ЊC);
[α]2D2 ϩ272.4 (c 1.0, CHCl3) {lit.47 [α]D ϩ279 (c 0.98, CHCl3)};
δH 1.38 (3 H, d, J 6.2, Me-5), 3.77 (1 H, dd, J 9.5 and 6.2, H-5),
3.90 (1 H, dd, J 13.3 and 1.2, H-1A), 4.28 (1 H, dd, J 13.3 and
2.1, H-1B), 5.54 (1 H, dd, J 10.0 and 3.6, H-3), 5.68 (1 H, [t],
J 10.0, H-4), 5.72 (1 H, m, H-2), 7.27 (2 H, m, Ph), 7.35–7.55
(6 H, complex, Ph), 7.60 (1 H, m, Ph), 7.84 (2 H, m, Ph), 7.97
(2 H, m, Ph), 8.10 (2 H, m, Ph); δC18.0, 68.1, 70.1, 71.9, 72.5,
75.4, 128.3, 128.4, 128.5, 129.1, 129.3, 129.7 (2 C), 129.9, 133.2,
133.3 (3 C), 165.7, 165.8, 165.8(4).
Methyl 2,3-di-O-acetyl-4-p-methoxybenzoyl-6-deoxy-ꢀ-D-
galactopyranoside 20
Mp 83–85 ЊC (from CH2Cl2–hexane); [α]2D2 ϩ117.1 (c 0.4,
CHCl3); δH1.20 (3 H, d, J 6.6, Me-5), 1.93 (3 H, s, Ac), 2.08
(3 H, s, Ac), 3.42 (3 H, s, OMe), 3.87 (3 H, s, OMe), 4.23 (1 H,
qd, J 6.7 and 2.3, H-5), 5.02 (1 H, d, J 3.6, H-1), 5.24 (1 H, dd,
J 10.8 and 3.6, H-2), 5.45 (1 H, dd, J 10.8 and 3.4, H-3), 5.52
(1 H, m, H-4), 6.94 (2 H, m, Ph), 8.06 (2 H, m, Ph); δC 16.0,
20.7, 20.9, 55.4, 55.5, 64.5, 68.1, 68.4, 71.2, 97.2, 113.8, 121.7,
131.9, 163.7, 165.8, 170.1, 170.5 (Found: C, 57.5; H, 6.1.
C19H24O9 requires C, 57.6; H, 6.1%).
Tri-O-benzoyl-2-deoxy-ꢁ-L-arabino-hexopyranose 39
Foam, [α]2D2 ϩ50.4 (c 1.01, CHCl3); δH 1.38 (3 H, d, J 6.2, Me-5),
2.20 (1 H, [t]d, J 12.0 and 9.9, H-2A), 2.73 (1 H, ddd, J 12.0, 5.3
and 2.3, H-2B), 3.96 (1 H, dq, J 9.5 and 6.2, H-5), 5.33 (1 H, [t],
J 9.4, H-4), 5.48 (1 H, ddd, J 10.4, 9.9 and 5.3, H-3), 6.20 (1 H,
dd, J 9.9 and 2.3, H-1), 7.39 (4 H, m, Ph), 7.46 (2 H, m, Ph),
7.51 (2 H, m, Ph), 7.59 (1 H, m, Ph), 7.97 (4 H, m, Ph), 8.10
(2 H, m, Ph); δC17.8, 35.4, 71.1, 71.4, 73.9, 91.6, 128.4, 128.5
(2 C), 129.1, 129.3, 129.4, 129.7 (2 C), 130.0, 133.2, 133.3,
133.6, 164.5, 165.7 (2 C) (Found: C, 70.2; H, 4.9. C27H24O7
requires C, 70.0; H, 5.0%).
1,5-Anhydro-tetra-O-benzoyl-D-glucitol 2743
This compound was formed as a minor product of the redox
rearrangement of the 1,2-benzylidene acetal 26 and was not
isolated. It was identified in the product mixture by its 1H NMR
spectrum,43 in particular from the presence of the characteristic
pseudo-triplet at δ 3.53 (J 10.7) arising from the axial proton
attached to C(1).
Methyl 2,4-di-O-benzoyl-3-deoxy-ꢁ-L-threo-pentopyranoside 47
Syrup, [α]2D2 ϩ152.6 (c 1.6, MeOH); δH 2.29 (1 H, m, H-3A), 2.43
(1 H, ddd, J 13.4, 12.2 and 3.3, H-3B), 3.48 (3 H, s, OMe), 3.82
(1 H, d[t], J 12.9 and 1.8, H-5A), 3.99 (1 H, dd, J 12.9 and 1.6,
H-5B), 5.04 (1 H, d, J 3.3, H-1), 5.35 (1 H, m, H-2), 5.48 (1 H,
ddd, J 12.2, 5.0 and 3.4, H-4), 7.36 (2 H, m, Ph), 7.45 (4 H, m,
Ph), 8.07 (2 H, m, Ph), 8.12 (2 H, m, Ph); δC 28.5, 55.5, 60.6,
67.4, 69.6, 96.7, 128.3(6), 128.4(2), 129.7(6), 129.7(9), 129.8(1),
133.2, 166.2 (Found: C, 67.6; H, 5.9. C20H20O6 requires C, 67.4;
H, 5.7%).
Tetra-O-benzoyl-2-deoxy-ꢀ-D-arabino-hexopyranose 2844
Mp 151–152 ЊC (from CH2Cl2–hexane) (lit.44 153–154 ЊC);
[α]2D3 ϩ53.1 (c 1.5, CHCl3) {lit.44 [α]2D2 ϩ68.6 (c 3.2, CHCl3)};
δH 2.29 (1 H, ddd, J 13.6, 11.5 and 3.6, H-2A), 2.72 (1 H, ddd,
J 13.6, 5.1 and 1.1, H-2B), 4.45 (1 H, dd, J 12.1 and 4.5, H-6A),
4.51 (1 H, ddd, J 10.0, 4.5 and 2.6, H-5), 4.58 (1 H, dd, J 12.1
and 2.6, H-6B), 5.74 (1 H, [t], J 9.8, H-4), 5.85 (1 H, ddd, J 11.5,
9.7 and 5.1, H-3), 6.62 (1 H, dd, J 3.6 and 1.1, H-1), 7.36 (6 H,
m, Ph), 7.50 (5 H, m, Ph), 7.63 (1 H, m, Ph), 7.95 (4 H, m, Ph),
8.00 (2 H, m, Ph), 8.15 (2 H, m, Ph); δC 34.5, 62.9, 69.5, 69.6,
70.8, 91.6, 128.3, 128.4(0), 128.4(2), 128.7, 129.0, 129.2(7),
129.3(2), 129.6(6), 129.7(0), 129.7(2), 129.8, 130.0, 133.0, 133.3,
133.4, 133.7, 164.5, 165.4, 165.9, 166.1.
Methyl 2,3-di-O-benzoyl-4-deoxy-ꢁ-L-threo-pentopyranoside
4848
Mp 101–102 ЊC (from hexane–diethyl ether) (lit.48a mp 102–103
ЊC), [α]1D8 ϩ207.1 (c 0.63, CHCl3); δH 1.98 (1 H, [t]dd, J 12.0, 11.0
and 5.4, H-4A), 2.32 (1 H, ddd, J 11.0, 5.3 and 2.0, H-4B), 3.42
(3 H, s, OMe), 3.74 (1 H, ddd, J 12.0, 5.3 and 2.0, H-5A), 3.95
(1 H, [t]d, J 12.0 and 2.5, H-5B), 5.09 (1 H, d, J 3.6, H-1), 5.26
(1 H, dd, J 10.0 and 3.6, H-2), 5.69 (1 H, ddd, J 11.0, 10.0 and
5.3, H-2), 7.37 (4 H, m, Ph), 7.50 (2 H, m, Ph), 7.97 (2 H, m,
1,5-Anhydro-tri-O-benzoyl-L-arabinitol 34
Mp 117–119 ЊC (from diethyl ether–hexane), [α]2D4 ϩ217.2 (c 1.3,
CHCl3). The -enantiomer45 shows mp 120–121 ЊC, [α]2D2 Ϫ219
(c 0.11, CHCl3). Compound 34 shows δH 3.68 (1 H, dd, J 11.8
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 3 3 0 – 1 3 4 1
1339