64
B. Grzeszczyk et al./Carbohydrate Research 307 (1998) 55±67
Methyl 2-O-allyl-3,4,7-tri-O-benzyl-d-glycero-
(CDCl3): ꢂ 101.9 (C-1), 76.07, 74.84, 73.69, 72.43,
and 68.03 (C-2,3,4,5,6); HR MS (LSIMS): Table 1.
Methyl 2,3,4,7-tetra-O-benzyl-l-glycero-a-d-
manno-heptopyranoside (28).Ð1H NMR (CDCl3):
ꢂ 4.70 (d, 1 H, H-1), 4.17 (dt, 1 H, H-6), 4.17 (t, 1
H, J4,5 9.6 Hz, H-4), 3.88 (dd, 1 H, J3,2 3.1, J3,4
9.4 Hz, H-3), 3.77 (dd, 1 H, J1,2 1.9 Hz, H-2), 3.56
(dd, 1 H, J7a,6 7.2, J7a,7b 9.5 Hz, H-7a), 3.65 (bd, 1
H, H-5), 3.57 (dd, 1 H, J7b,6 6.0 Hz, H-7b); 13C
NMR (CDCl3): Table 2. HR MS (LSIMS): Table 1.
The d-glycero-d-manno stereoisomer (30) was
characterized as its 6-O-acetyl derivative.
Methyl 6-O-acetyl-2,3,4,7-tetra-O-benzyl-d-
glycero-a-d-manno-heptopyranoside.Ð1H NMR
(CDCl3): ꢂ 5.56 (ddd, 1 H, J6,5 2.0, J6,7a 4.6 Hz, H-
6), 4.71 (bs, 1 H, H-1), 3.98 (t, 1 H, H-4), 3.86 (dd,
1 H, J3,4 9.0, J3,2 3.0 Hz, H-3), 3.80 (dd, 1 H, J5,4
9.9 Hz, H-5), 3.76 (dd, 1 H, J7a,7b 10.7 Hz, H-7a),
3.74 (dd, 1 H, H-2), 3.68 (dd, 1 H, J7b,6 7.2, H-7b);
13C NMR (CDCl3): ꢂ 98.69 (C-1), 80.22 (C-3),
74.74, 74.66, 71.76, and 71.67 (C-2,4,5,6), 68.18 (C-
7). HR-MS (LSIMS): Table 1.
Methyl 7-O-allyl-2,3,4-tri-O-benzyl-d(l)-gly-
cero-b-l-gulo-heptopyranoside (37).Ð1H NMR
(CDCl3): ꢂ 4.70 (d, 1 H, J1,2 8.2 Hz, H-1), 3.80 (dd,
1 H, J5,6 9.0, J5,4 0.9 Hz, H-5), 3.71 (t, 1 H, J3,4
3.8 Hz, H-3), 3.70 (dd, 1 H, H-4), 3.66 (dd, 1 H,
J7a,6 3.1, J7a,7b 9.7 Hz, H-7a), 3.57 (dd, 1 H, J7b,6
5.7 Hz, H-7b), 3.56 (dd, 1 H, J2,3 2.7 Hz, H-2); 13C
NMR (CDCl3): ꢂ 101.9 (C-1), 76.10, 74.88, 73.76,
72.56, and 67.94 (C-2,3,4,5,6), 71.10 (C-7). HR MS
(LSIMS): Table 1.
Methyl 7-O-allyl-2,3,4-tri-O-benzyl-l-glycero-
a-d-manno-heptopyranoside (32).Ð1H NMR
(CDCl3): ꢂ 4.71 (bs, 1 H, H-1), 4.17 (t, 1 H, H-4),
4.14 (bt, 1 H, H-6), 3.88 (dd, 1 H, J3,2 3.1, J3,4
9.5 Hz, H-3), 3.78 (dd, 1 H, J2,1 1.9 Hz, H-2), 3.64
(dd, 1 H, J5,6 1.0, J5,4 9.8 Hz, H-5), 3.60 (dd, 1 H,
J7a,6 7.3, J7a,7b 9.5 Hz, H-7a), 3.52 (dd, 1 H, J7b,6
6.0 Hz, H-7b); 13C NMR: Table 2. HR MS
(LSIMS): Table 1.
a-d-manno-heptopyranoside (14).Ð1H NMR
(CDCl3): ꢂ 4.68 (d, 1 H, J1,2 2.1 Hz, H-1), 3.94 (t, 1
H, J2,3 2.5 Hz, H-2), 3.67 (dd, 1 H, J7a,6 6.7, J7a,7b
10.1 Hz, H-7a), 3.60 (dd, 1 H, J7b,6 3.1, H-7b); 13C
NMR (CDCl3): ꢂ 99.09 (C-1), 80.25 (C-3), 76.07,
74.40, 71.99, and 71.01 (C-2,4,5,6), 70.82 (C-7).
Methyl 3-O-allyl-2,4,7-tri-O-benzyl-d(l)-gly-
cero-b-l-gulo-heptopyranoside (21).Ð1H NMR
(CDCl3): ꢂ 4.62 (d, 1 H, J1,2 8.2 Hz, H-1), 3.78 (dd,
1 H, J5,6 9.0, J5,4 1.2 Hz, H-5), 3.71 (dd, 1 H, J4,5
1.4, J4,3 3.7 Hz, H-4), 3.71 (dd, 1 H, J7a,6 3.1, J7a,7b
9.8 Hz, H-7a), 3.63 (t, 1 H, J3,2 3.3 Hz, H-3), 3.63
(dd, 1 H, J7b,6 5.5 Hz, H-7b), 3.53 (dd, 1 H, H-2);
13C NMR (CDCl3): ꢂ 101.8 (C-1), 75.85, 74.88,
73.79, 72.48, and 68.00 (C-2,3,4,5,6), 71.17 (C-7).
HR MS (LSIMS): Table 1.
Methyl 3-O-allyl-2,4,7-tri-O-benzyl-l-glycero-
a-d-manno-heptopyranoside (16).Ð1H NMR
(CDCl3): ꢂ 4.69 (bs, 1 H, H-1), 4.12 (t, 1 H, H-4),
3.76 (dd, 1 H, J3,2 3.1, J3,4 9.3 Hz, H-3), 3.74 (dd,
J2,1 1.8 Hz, H-2), 3.65 (dd, 1 H, J7a,6 7.2, J7a,7b
9.5 Hz, H-7a), 3.63 (dd, 1 H, J5,6 1.0, J5,4 9.8 Hz,
H-5), 3.57 (dd, 1 H, J7b,6 6.0 Hz, H-7b); 13C NMR
(CDCl3): Table 2. HR MS (LSIMS): Table 1.
Methyl 3-O-allyl-2,4,7-tri-O-benzyl-d-glycero-ꢀ-
d-manno-heptopyranoside (20) was not isolated in
analytically pure state.
Methyl 2,3,7-tri-O-benzyl-4-O-(p-methoxybenzyl)-
d(l)-glycero-b-l-gulo-heptopyranoside (27).Ð1H
NMR (CDCl3): ꢂ 4.67 (d, 1 H, J1,2 8.2 Hz, H-1),
4.02 (ddd, 1 H, J6,5 8.7, J6,7a 3.1, J6,7b 5.4 Hz, H-6),
3.81 (dd, 1 H, J5,4 1.0 Hz, H-5), 3.97 (t, 1 H, J3,4
3.6 Hz, H-3), 3.62 (dd, 1 H, J7b,7a 9.7 Hz, H-7b),
3.53 (dd, 1 H, J2,3 2.7 Hz, H-2); 13C NMR (CDCl3):
ꢂ 101.8 (C-1), 76.10, 74.81, 73.25, 72.41, and 68.06
(C-2,3,4,5,6), 71.16 (C-7). HR MS (LSIMS):
Table 1.
Methyl 2,3,7-tri-O-benzyl-4-O-(p-methoxybenzyl)-
l-glycero-a-d-manno-heptopyranoside (23).Ð1H
NMR (CDCl3): ꢂ 4.62 (d, 1 H, J1,2 1.7 Hz, H-1),
4.09 (dt, 1 H, J6,5 1.1 Hz, H-6), 4.08 (t, 1 H, J4,5
9.6 Hz, H-4), 3.79 (dd, 1 H, J3,2 3.1, J3,4 9.5 Hz, H-
3), 3.70 (dd, 1 H, H-2), 3.58 (dd, 1 H, J7a,6 7.3,
J7a,7b 9.4 Hz, H-7a), 3.55 (dd, 1 H, H-5), 3.49 (dd, 1
H, J7b,6 5.9 Hz, H-7b); 13C NMR (CDCl3): Table 2.
HR MS (LSIMS): Table 1.
The d-glycero-ꢀ-d-manno (36) stereoisomer was
characterized as its 6-O-acetyl derivative
Methyl 6-O-acetyl-7-O-allyl-2,3,4-tri-O-benzyl-
d-glycero-a-d-manno-heptopyranoside.Ð1H NMR
(CDCl3): ꢂ 5.50 (ddd, 1 H, J6,5 2.1, J6,7a 4.8, J6,7b
6.9 Hz, H-6), 4.72 (bs, 1 H, H-1), 3.99 (t, 1 H, H-4),
3.87 (dd, 1 H, J3,2 3.1, J3,4 9.1 Hz, H-3), 3.79 (dd, 1 H,
J5,4 9.9 Hz, H-5), 3.75 (dd, 1 H, J2,1 1.8 Hz, H-2), 3.74
(dd, 1 H, J7a,7b 10.7 Hz, H-7a), 3.64 (dd, 1 H, H-7b);
13C NMR (CDCl3): ꢂ 90.06 (C-1), 80.64 (C-3), 75.14,
75.06, 72.12, and 72.04 (C-2,4,5,6), 68.34 (C-7).
Methyl 2,3,4,7-tetra-O-benzyl-d(l)-glycero-b-l-
gulo-heptopyranoside (31).Ð1H NMR (CDCl3): ꢂ
4.68 (d, 1 H, J1,2 8.2 Hz, H-1), 4.04 (ddd, 1 H, J6,7a
3.1, J6,7b 5.3, J6,5 9.0 Hz, H-6), 3.82 (dd, 1 H, H-5),
3.65 (dd, 1 H, J7a,7b 9.5 Hz, H-7b); 13C NMR