disc) 2577 cmϪ1 (SH str.). (Found: C, 54.4; H, 3.1. C34H24Cl4O9S
requires C, 54.4; H, 3.2%).
The characteristics of the remaining α-glucosyl bromides and
the glucose thiols are given below. The yields of pyranosyl
bromides are based on penta-O-aroylglucose and those of the
thiols are based on the pyranosyl bromide.
H-1), 7.21–8.94 (28 H, m, Np); δC 62.2, 68.1, 70.6, 71.6, 72.9,
87.2, 124.4, 124.6 (3 C), 125.2, 125.4 (3 C), 125.9 (2 C), 126.1
(2 C), 126.2, 126.3 (3 C), 127.6, 127.9, 128.0, 128.2, 128.3, 128.5
(2 C), 128.6, 130.1, 130.7, 130.8, 131.1, 131.4 (2 C), 131.5,
131.7, 133.5, 133.6, 133.7 (2 C), 133.8 (2 C), 134.2, 134.5, 165.7,
165.8, 166.4, 166.8. (Found: C, 70.1; H, 4.3. C50H35BrO9
requires C, 69.9; H, 4.1%).
1-Bromo-2,3,4,6-tetra-O-(2-chlorobenzoyl)-ꢁ-D-glucopyranose
10b. Foam, yield 82%, [α]1D9 ϩ113.3 (c 2.0, CHCl3); δH 4.64 (2 H,
m, H-6), 4.69 (1 H, m, H-5), 5.32 (1 H, dd, J 9.9 and 4.1, H-2),
5.81 (1 H, t, J 9.9, H-4), 6.23 (1 H, t, J 9.8, H-3), 6.87 (1 H, d,
J 4.0, H-1), 7.23–7.96 (16 H, m, Ph); δC 62.6, 68.1, 70.8, 71.5,
72.3, 86.2, 126.7(0), 126.7(2), 126.7(4), 126.8, 127.3, 128.6,
128.7, 129.2, 131.0, 131.1(1), 131.1(3), 131.4(0), 131.4(1), 131.5,
131.7, 132.4, 132.9, 133.0, 133.2, 133.6, 133.8, 133.9, 134.0,
134.8, 163.5, 164.1, 164.4, 164.9. (Found: C, 51.0; H, 2.7.
C34H23BrCl4O9 requires C, 51.2; H, 2.9%).
1-Bromo-2,3,4,6-tetra-O-(2-naphthoyl)-ꢁ-D-glucopyranose
10i. Foam, yield 83%, [α]1D9 ϩ105.4 (c 2.0, CHCl3); δH 4.68 (1 H,
dd, J 12.4 and 4.6, HA-6), 4.80 (1 H, dd, J 12.4 and 3.1, HB-6),
4.91 (1 H, m, H-5), 5.51 (1 H, dd, J 9.9 and 4.1, H-2), 6.01 (1 H,
t, J 10.0, H-4), 6.47 (1 H, t, J 9.8, H-3), 7.00 (1 H, d, J 4.1, H-1),
7.43–8.62 (28 H, m, Np); δC 62.4, 68.6, 71.0, 71.7, 72.8, 87.0,
125.0, 125.1 (2 C), 125.2, 125.6, 125.8, 126.0, 126.5 (2 C), 126.7
(3 C), 127.5, 127.6, 127.7 (2 C), 128.2 (2 C), 128.3 (2 C), 128.4
(2 C), 128.5, 128.6, 129.4 (2 C), 129.5 (2 C), 131.5 (2 C), 131.8,
132.1, 132.2, 132.3, 132.4 (2 C), 135.6 (2 C), 135.7, 135.9, 165.3,
165.5, 165.8, 166.2. (Found: C, 69.8; H, 4.0. C50H35BrO9
requires C, 69.9; H, 4.1%).
1-Bromo-2,3,4,6-tetra-O-(2-bromobenzoyl)-ꢁ-D-glucopyranose
10d. Foam, yield 79%, [α]1D9 ϩ93.7 (c 2.0, CHCl3); δH 4.64 (2 H,
m, H-6), 4.70 (1 H, m, H-5), 5.32 (1 H, dd, J 9.9 and 4.1, H-2),
5.81 (1 H, t, J 9.9, H-4), 6.23 (1 H, t, J 9.7, H-3), 6.87 (1 H, d,
J 4.1, H-1), 7.28–7.98 (16 H, m, Ph); δC 62.3, 68.2, 70.8, 71.5,
72.2, 86.2, 121.8, 121.9 (2 C), 122.7, 127.3 (2 C), 127.4, 127.5,
129.1, 130.6 (2 C), 131.2, 131.5, 131.6, 131.7, 132.5, 132.9,
133.1, 133.2, 133.6, 134.3 (2 C), 134.4, 134.7, 164.0, 164.6,
164.8, 165.4. (Found: C, 42.2; H, 2.3. C34H23Br5O9 requires C,
41.9; H, 2.4%).
2,3,4,6-Tetra-O-benzoyl-1-thio-ꢀ-D-glucopyranose 11a. Foam,
yield 67%, [α]2D3 ϩ62.1 (c 2.0, CHCl3); δH 2.48 (1 H, d, J 9.8, SH),
4.18 (1 H, m, H-5), 4.48 (1 H, dd, J 12.3 and 5.0, HA-6), 4.63
(1 H, dd, J 12.3 and 2.9, HB-6), 4.90 (1 H, t, J 9.8, H-1), 5.51
(1 H, t, J 9.6, H-2), 5.72 (1 H, t, J 9.8, H-4), 5.89 (1 H, t, J 9.6,
H-3), 7.26–8.05 (20 H, m, Ph); δC 63.1, 69.4, 73.8, 74.2, 76.7,
79.1, 128.2 (2 C), 128.3 (2 C), 128.4 (4 C), 128.7, 129.0, 129.6
(3 C), 129.7 (5 C), 129.8 (2 C), 133.1, 133.2, 133.4 (2 C), 165.1,
165.4, 165.7, 166.1; IR (KBr disc) 2560 cmϪ1 (SH str.). (Found:
C, 66.6; H, 4.5. C34H28O9S requires C, 66.7; H, 4.6%).
1-Bromo-2,3,4,6-tetra-O-(3-bromobenzoyl)-ꢁ-D-glucopyranose
10e. Foam, yield 85%, [α]1D9 ϩ79.5 (c 1.9, CHCl3); δH 4.54 (1 H,
dd, J 12.6 and 4.4, HA-6), 4.64 (1 H, dd, J 12.6 and 2.9, HB-6),
4.72 (1 H, dt, J 10.0 and 3.7, H-5), 5.31 (1 H, dd, J 10.0 and 4.1,
H-2), 5.74 (1 H, t, J 10.0, H-4), 6.19 (1 H, t, J 9.8, H-3), 6.84
(1 H, d, J 4.1, H-1), 7.20–8.16 (16 H, m, Ph); δC 62.2, 68.3, 71.0,
71.5, 72.3, 86.2, 122.5 (2 C), 122.6 (2 C), 128.2, 128.3, 128.4,
128.5, 130.0 (2 C), 130.1 (4 C), 130.3, 131.1, 132.7 (3 C), 132.9,
136.2, 136.5, 136.7, 136.8, 163.7, 163.9, 164.2, 164.6. (Found: C,
41.8; H, 2.2. C34H23Br5O9 requires C, 41.9; H, 2.4%).
2,3,4,6-Tetra-O-(2-chlorobenzoyl)-1-thio-ꢀ-D-glucopyranose
11b. Foam, yield 66%, [α]2D0 ϩ23.7 (c 2.0, CHCl3); δH 2.50 (1 H,
d, J 10.0, SH), 4.15 (1 H, m, H-5), 4.57 (1 H, dd, J 12.4 and 4.8,
HA-6), 4.63 (1 H, dd, J 12.4 and 2.7, HB-6), 4.85 (1 H, t, J 9.9,
H-1), 5.49 (1 H, t, J 9.6, H-2), 5.72 (1 H, t, J 9.8, H-4), 5.88
(1 H, t, J 9.5, H-3), 7.25–7.94 (16 H, m, Ph); δC 63.2, 69.4, 73.8,
74.3, 76.3, 78.9, 126.6(4), 126.6(6), 126.6(9), 126.7(4), 128.4,
128.6, 128.8, 129.3, 130.9(5), 131.0(0), 131.0(3), 131.0(6), 131.5
(2 C), 131.6, 131.7, 132.8, 133.1 (3 C), 133.8, 133.9 (2 C), 134.0,
164.1, 164.2, 164.4, 165.0; IR (KBr disc) 2561 cmϪ1 (SH str.).
(Found: C, 54.1; H, 3.1. C34H24Cl4O9S requires C, 54.4; H,
3.2%).
1-Bromo-2,3,4,6-tetra-O-(2-methylbenzoyl)-ꢁ-D-gluco-
pyranose 10f. Foam, yield 79%, [α]1D9 ϩ115.1 (c 2.0, CHCl3);
δH 2.34 (3 H, s, Me), 2.46 (3 H, s, Me), 2.56 (3 H, s, Me), 2.62
(3 H, s, Me), 4.57 (2 H, m, H-6), 4.70 (1 H, dt, J 10.2 and 3.6,
H-5), 5.30 (1 H, dd, J 10.0 and 4.0, H-2), 5.76 (1 H, t, J 10.0,
H-4), 6.25 (1 H, t, J 9.8, H-3), 6.89 (1 H, d, J 4.0, H-1),
7.10–8.00 (16 H, m, Ph); δC 21.2, 21.5, 21.7, 21.9, 61.7, 67.7,
70.2, 71.3, 72.8, 87.2, 125.7, 125.8 (2 C), 125.9, 127.3, 127.8,
128.3, 128.9, 130.5, 130.8 (2 C), 131.5, 131.6, 131.7, 131.8,
132.2, 132.3, 132.6, 132.8, 132.9, 140.3, 140.4, 140.9, 141.3,
165.5, 165.8, 166.2, 166.9. (Found: C, 64.1; H, 5.0. C38H35BrO9
requires C, 63.8; H, 4.9%).
2,3,4,6-Tetra-O-(2-bromobenzoyl)-1-thio-ꢀ-D-glucopyranose
11d. Foam, yield 69%, [α]2D1 ϩ16.2 (c 2.0, CHCl3); δH 2.51 (1 H,
d, J 10.1, SH), 4.14 (1 H, m, H-5), 4.57 (1 H, dd, J 12.4 and 4.8,
HA-6), 4.64 (1 H, dd, J 12.4 and 2.7, HB-6), 4.85 (1 H, t, J 9.9,
H-1), 5.49 (1 H, t, J 9.6, H-2), 5.72 (1 H, t, J 9.8, H-4), 5.88
(1 H, t, J 9.5, H-3), 7.29–7.82 (16 H, m, Ph); δC 63.4, 69.5, 73.9,
74.4, 76.3, 79.0, 121.8(7), 121.9(1), 122.0(8), 122.1(1), 127.2(6)
(2 C), 127.2(9), 127.4, 130.2, 130.6, 130.7, 131.4, 131.6,
131.7(0), 131.7(3), 131.9, 132.8, 133.1(1), 133.1(5), 133.2(1),
134.3(3) (2 C), 134.3(7), 134.4(2), 164.6, 164.7, 164.8, 165.5;
IR (KBr disc) 2557 cmϪ1 (SH str.). (Found: C, 43.8; H, 2.6.
C34H24Br4O9S requires C, 44.0; H, 2.6%).
1-Bromo-2,3,4,6-tetra-O-(3-methylbenzoyl)-ꢁ-D-gluco-
pyranose 10g. Foam, yield 81%, [α]1D9 ϩ102.9 (c 2.0, CHCl3);
δH 2.29 (3 H, s, Me), 2.34 (3 H, s, Me), 2.35 (3 H, s, Me), 2.40
(3 H, s, Me), 4.51 (1 H, dd, J 12.5 and 4.6, HA-6), 4.63 (1 H, dd,
J 12.5 and 2.8, HB-6), 4.72 (1 H, m, H-5), 5.29 (1 H, dd, J 10.0
and 4.0, H-2), 5.78 (1 H, t, J 10.0, H-4), 6.25 (1 H, t, J 9.8, H-3),
6.87 (1 H, d, J 4.0, H-1), 7.19–7.86 (16 H, m, Ph); δC 21.0 (2 C),
21.1, 21.2, 61.9, 68.0, 70.5, 71.5, 72.7, 86.9, 126.8, 126.9, 127.0,
127.1, 128.1, 128.3 (3 C), 128.4 (2 C), 128.7, 129.3, 130.1, 130.2,
130.3, 130.5, 133.9, 134.0, 134.3, 134.5, 138.0, 138.1, 138.2
(2 C), 165.1, 165.4, 165.6, 166.1. (Found: C, 64.1; H, 5.1.
C38H35BrO9 requires C, 63.8; H, 4.9%).
2,3,4,6-Tetra-O-(3-bromobenzoyl)-1-thio-ꢀ-D-glucopyranose
11e. Foam, yield 65%, [α]2D1 ϩ36.0 (c 2.0, CHCl3); δH 2.47 (1 H,
d, J 10.1, SH), 4.18 (1 H, m, H-5), 4.51 (1 H, dd, J 12.3 and 4.8,
HA-6), 4.59 (1 H, dd, J 12.3 and 3.3, HB-6), 4.89 (1 H, t, J 9.8,
H-1), 5.47 (1 H, t, J 9.6, H-2), 5.65 (1 H, t, J 9.8, H-4), 5.83
(1 H, t, J 9.5, H-3), 7.18–8.13 (16 H, m, Ph); δC 63.3, 69.7, 74.2,
74.4, 76.3, 79.0, 122.4(9) (2 C), 122.5(8), 122.6(0), 128.2,
128.3(0), 128.3(4), 128.4, 129.9(8), 130.0(2), 130.0(7) (2 C),
130.2(7), 130.2(9), 130.6, 131.2, 132.6(6), 132.7(0) (2 C), 132.8,
136.2, 136.5, 136.6(1), 136.6(4), 163.8, 164.1, 164.4, 164.8; IR
(KBr disc) 2561 cmϪ1 (SH str.). (Found: C, 43.9; H, 2.4.
C34H24Br4O9S requires C, 44.0; H, 2.6%).
1-Bromo-2,3,4,6-tetra-O-(1-naphthoyl)-ꢁ-D-glucopyranose
10h. Foam, yield 85%, [α]1D9 ϩ125.7 (c 1.7, CHCl3); δH 4.77 (1 H,
dd, J 12.5 and 2.9, HA-6), 4.82 (1 H, dd, J 12.5 and 4.4, HB-6),
4.91 (1 H, m, H-5), 5.54 (1 H, dd, J 10.0 and 4.0, H-2), 6.05
(1 H, t, J 10.0, H-4), 6.54 (1 H, t, J 9.8, H-3), 7.07 (1 H, d, J 4.0,
1382
J. Chem. Soc., Perkin Trans. 1, 2002, 1376–1386