H. Jona et al.
Bull. Chem. Soc. Jpn., 75, No. 2 (2002) 305
H), 3.70–3.82 (m, 3 H), 3.88–3.97 (m, 3 H), 3.96 (dd, J = 9.8, 9.2
Hz, 1 H), 4.03 (dd, J = 8.5, 3.4 Hz, 1 H), 4.36 (d, J = 11.9 Hz, 1
H), 4.43 (d, J = 11.9 Hz, 1 H), 4.53 (d, J = 3.4 Hz, 1 H, H-1),
4.55 (d, J = 12.5 Hz, 1 H), 4.56 (d, J = 12.5 Hz, 1 H), 4.58 (d, J
= 10.7 Hz, 1 H), 4.67–4.75 (m, 4 H), 4.78 (d, J = 11.9 Hz, 1 H),
4.80 (d, J = 11.0 Hz, 1 H), 4.85 (d, J = 10.7 Hz, 1 H), 4.93 (d, J
= 12.5 Hz, 1 H), 4.95 (d, J = 11.0 Hz, 1 H), 4.99 (d, J = 3.4 Hz,
1 H, H-1ꢀ), 7.18–7.37 (m, 35 H); 13C NMR (125 MHz, CDCl3) δ
55.3, 66.6, 69.2, 69.6, 70.5, 72.8, 73.0, 73.5, 75.0, 75.2, 75.3,
75.9, 77.5, 78.2, 78.5, 80.4, 82.3, 98.1 (C-1), 98.2 (C-1ꢀ), 127.57,
127.64, 127.7, 127.86, 127.91, 128.0, 128.2, 128.42, 128.46,
128.51, 128.56, 128.58, 128.62, 138.3, 138.4, 138.7, 138.95,
138.98, 139.09, 139.12; HRMS m/z calcd for C62H70NO11 [M +
NH4]+ 1004.4949, found 1004.4956.
20β: White solid. Mp 126–128 ˚C; Rf = 0.4 (hexane/EtOAc =
2/1), 0.29 (hexane/CHCl3/acetone = 20/20/1, 2 times); [α]D21 +12
(c 1.0, CHCl3); IR (KBr) 2916, 2862, 1458, 1358, 1103, 1065,
741, 694 cm−1; 1H NMR (500 MHz, CDCl3) δ 3.29 (s, 3 H), 3.46
(dd, J = 10.1, 9.5 Hz, 1 H), 3.47–3.53 (m, 3 H), 3.56 (dd, J = 9.2,
5.5 Hz, 1 H), 3.57–3.64 (m, 2 H), 3.78–3.86 (m, 1 H), 3.84 (dd, J
= 9.8, 7.6 Hz, 1 H), 3.86–3.92 (m, 1 H), 3.97 (dd, J = 9.5, 9.2 Hz,
1 H), 4.13 (dd, J = 9.5, 1.5 Hz, 1 H), 4.30 (d, J = 7.6 Hz, 1 H, H-
1ꢀ), 4.40 (d, J = 11.6 Hz, 1 H), 4.41 (d, J = 11.6 Hz, 1 H), 4.50 (d,
J = 11.3 Hz, 1 H), 4.57 (d, J = 11.3 Hz, 1 H), 4.58 (d, J = 3.4 Hz,
1 H, H-1), 4.64 (d, J = 12.2 Hz, 1 H), 4.68–4.80 (m, 6 H), 4.92 (d,
J = 11.3 Hz, 1 H), 4.93 (d, J = 11.6 Hz, 1 H), 4.95 (d, J = 11.0
Hz 1 H), 7.14–7.38 (m, 35 H); 13C NMR (125 MHz, CDCl3) δ
55.1, 68.5, 68.6, 69.9, 72.9, 73.3, 73.5, 74.5, 74.8, 75.1, 75.6,
78.1, 79.2, 79.9, 82.0, 82.3, 97.9 (C-1), 104.2 (C-1ꢀ), 127.3, 127.4,
127.5, 127.65, 127.76, 127.85, 127.93, 127.97, 128.10, 128.11,
128.20, 128.25, 128.30, 128.32, 128.4, 137.9, 138.2, 138.4, 138.5,
138.71, 138.73, 138.9; HRMS m/z calcd for C62H70NO11 [M +
NH4]+ 1004.4949, found 1004.4966.
(500 MHz, CDCl3) δ 3.28–3.42 (m, 3 H), 3.37 (s, 3 H), 3.47 (dd, J
= 9.8, 3.7 Hz, 1 H), 3.47–3.55 (m, 2 H), 3.57–3.62 (m, 1 H), 3.74
(dd, J = 9.5, 7.6 Hz, 1 H), 3.79–3.85 (m, 2 H), 3.86–3.94 (m, 2
H), 4.24 (d, J = 11.9 Hz, 1 H), 4.30 (d, J = 7.6 Hz, 1 H, H-1ꢀ),
4.33 (d, J = 11.9 Hz, 1 H), 4.36 (d, J = 11.9 Hz, 1 H), 4.53 (d, J
= 11.9 Hz, 1 H), 4.55 (d, J = 11.3 Hz, 1 H), 4.56 (d, J = 3.7 Hz,
1 H, H-1), 4.63 (d, J = 12.2 Hz, 1 H), 4.67 (d, J = 11.6 Hz, 1 H),
4.71 (d, J = 11.6 Hz, 1 H), 4.72 (d, J = 10.7 Hz, 1 H), 4.76 (d, J
= 11.3 Hz, 1 H), 4.80 (d, J = 11.3 Hz, 1 H), 4.82 (d, J = 12.2 Hz,
1 H), 4.96 (d, J = 11.3 Hz, 1 H), 5.02 (d, J = 10.7 Hz 1 H), 7.10–
7.39 (m, 35 H); 13C NMR (125 MHz, CDCl3) δ 55.3, 68.0, 68.2,
70.0, 72.6, 73.09, 73.13, 73.4, 73.7, 73.8, 74.7, 75.2, 75.5, 76.6,
78.9, 80.1, 80.3, 82.5, 98.4 (C-1), 102.8 (C-1ꢀ), 127.0, 127.36,
127.39, 127.50, 127.53, 127.6, 127.7, 127.8, 127.9, 128.06,
128.12, 128.16, 128.18, 128.29, 128.33, 128.36, 138.1, 138.2,
138.5, 138.9, 139.0, 139.4; HRMS m/z calcd for C62H70NO11 [M
+ NH4]+ 1004.4949, found 1004.4955.
Methyl 6-O-[2ꢀ,3ꢀ,4ꢀ-Tri-O-benzoyl-6ꢀ-O-(2ꢁ,3ꢁ,4ꢁ,6ꢁ-tetra-
α
β
O-benzyl- -D-glucopyranosyl)- -D-glucopyranosyl]-2,3,4-tri-
α β
α
O-benzyl- -D-glucopyranoside (22 ꢀ ) and Methyl 6-O-
[2ꢀ,3ꢀ,4ꢀ-Tri-O-benzoyl-6ꢀ-O-(2ꢁ,3ꢁ,4ꢁ,6ꢁ-tetra-O-benzyl- -D-
glucopyranosyl)- -D-glucopyranosyl]-2,3,4-tri-O-benzyl- -D-
glucopyranoside (22 ꢀ ): These compounds were synthesized
β
β
α
β β
from glycosyl donor 1, glycosyl acceptor 6 and 2 according to
method D: 93%, α/β = 85/15, method E: 88%, α/β = 87/13,
method F: 93%, α/β = 7/93. The ratios were determined by isola-
tion of each isomer (hexane/EtOAc).
22αꢀβ: foam; Rf = 0.5 (hexane/EtOAc = 6/4); [α]D23 +23 (c 2.4,
CHCl3); IR (KBr) 2931, 2908, 2862, 1736, 1450, 1365, 1265,
1095, 741, 702 cm−1; 1H NMR (500 MHz, CDCl3) δ 3.03 (s, 3H),
3.34–3.43 (m, 2 H), 3.51 (dd, J = 9.8, 3.4 Hz, 1 H), 3.52–3.58 (m,
1 H), 3.58–3.66 (m, 4 H), 3.73 (dd, J = 10.7, 3.4 Hz, 1 H), 3.78–
3.83 (m, 1 H), 3.83 (dd, J = 9.5, 9.2 Hz, 1 H), 3.87 (dd, J = 11.3,
6.7 Hz, 1 H), 3.91 (dd, J = 9.8, 9.2 Hz, 1 H), 4.01–4.07 (m, 1 H),
4.10 (d, J = 10.4 Hz, 1 H), 4.20 (d, J = 11.3 Hz, 1 H), 4.35 (d, J
= 12.2 Hz, 1 H), 4.38 (d, J = 11.3 Hz, 1 H), 4.44 (d, J = 11.3 Hz,
1 H), 4.45 (d, J = 3.7 Hz, 1 H, H-1), 4.54 (d, J = 12.2 Hz, 1 H),
4.56 (d, J = 12.2 Hz, 1 H), 4.59 (d, J = 12.2 Hz, 1 H), 4.65 (d, J
= 11.3 Hz, 1 H), 4.69 (d, J = 12.2 Hz, 1 H), 4.71 (d, J = 10.4 Hz,
1 H), 4.71 (d, J = 10.4 Hz, 1 H), 4.72 (d, J = 3.4 Hz, 1 H, H-1ꢁ),
4.76 (d, J = 7.9 Hz, 1 H, H-1ꢀ), 4.80 (d, J = 11.3 Hz, 1 H), 4.86
(d, J = 10.4 Hz, 1 H), 4.87 (d, J = 10.4 Hz, 1 H), 5.48 (dd, J =
9.8, 9.8 Hz, 1 H), 5.53 (dd, J = 9.5, 7.9 Hz, 1 H), 5.83 (dd, J =
9.8, 9.5 Hz, 1 H), 6.99 (d, J = 7.0 Hz, 2 H), 7.08–7.13 (m, 2 H),
7.14–7.43 (m, 39 H), 7.48 (dd, J = 7.9, 7.9 Hz, 1 H), 7.79 (d, J =
7.9 Hz, 2 H), 7.87 (d, J = 7.9 Hz, 2 H), 7.92 (d, J = 7.9 Hz, 2 H);
13C NMR (125 MHz, CDCl3) δ 54.9, 67.1, 67.8, 68.4, 69.4, 69.8,
70.2, 71.9, 73.0, 73.1, 73.36, 73.40, 74.5, 74.8, 75.4, 75.5, 77.1,
77.4, 79.7, 80.1, 81.75, 81.82, 97.3 (C-1ꢁ), 97.9 (C-1), 100.8 (C-
1ꢀ), 127.30, 127.37, 127.47, 127.55, 127.62, 127.79, 127.80,
127.83, 127.87, 128.02, 128.08, 128.18, 128.24, 128.27, 128.30,
128.4, 128.8, 128.9, 129.2, 129.7, 129.8, 133.0, 133.1, 133.3,
138.1, 138.25, 138.28, 138.43, 138.8, 164.8, 165.1, 165.8; HRMS
m/z calcd for C89H92NO19 [M + NH4]+ 1478.6264, found
1478.6271.
Methyl 2,3,6-Tri-O-benzyl-4-O-(2ꢀ,3ꢀ,4ꢀ,6ꢀ-tetra-O-benzyl-D-
53
α
galactopyranosyl)- -D-glucopyranoside (21):
This com-
pound was synthesized from glycosyl donor 15 and glycosyl ac-
ceptor 5 according to method A: 7.5 h, 96%, α/β = 93/7, method
B: 15.5 h, 93%, α/β = 93/7, method C: 2 h, > 99%, α/β = 27/73.
1
The ratios were determined by H-NMR analysis. Both anomers
were partially separated by thin-layer chromatography (hexane/
CHCl3/acetone).
21α: foam; Rf = 0.5 (hexane/EtOAc = 2/1), 0.39 (hexane/
CHCl3/acetone = 20/20/1, 2 times); [α]D23 +33 (c 1.3, CHCl3); IR
1
(KBr) 2934, 1458, 1358, 1103, 1041, 741, 702 cm−1; H NMR
(500 MHz, CDCl3) δ 3.37 (s, 3 H), 3.40–3.52 (m, 2 H), 3.54 (dd, J
= 9.5, 3.4 Hz, 1 H), 3.63–3.68 (m, 1 H), 3.70 (dd, J = 10.4, 4.3
Hz, 1 H), 3.78–3.89 (m, 3 H), 3.91–3.98 (m, 2 H), 3.98 (dd, J =
10.7, 4.0 Hz, 1 H), 4.06 (dd, J = 9.5, 8.9 Hz, 1 H), 4.24 (d, J =
11.6 Hz, 1 H), 4.30 (d, J = 11.6 Hz, 1 H), 4.42 (d, J = 12.2 Hz, 1
H), 4.51–4.56 (m, 3 H), 4.57 (d, J = 3.4 Hz, 1 H, H-1), 4.59 (d, J
= 12.5 Hz, 1 H), 4.61–4.72 (m, 4 H), 4.81 (d, J = 11.3 Hz, 1 H),
4.86 (d, J = 11.3 Hz, 1 H), 4.96 (d, J = 11.3 Hz, 1 H), 5.75 (d, J
= 4.0 Hz, 1 H, H-1ꢀ), 7.15–7.33 (m, 35 H); 13C NMR (125 MHz,
CDCl3) δ 55.1, 68.7, 69.43, 69.48, 69.9, 72.7, 72.8, 73.1, 73.3,
73.4, 73.8, 74.3, 74.66, 74.75, 75.6, 79.2, 80.2, 82.0, 97.5 (C-1ꢀ),
97.7 (C-1), 126.7, 127.0, 127.36, 127.42, 127.50, 127.55, 127.66,
127.8, 127.9, 128.14, 128.19, 128.25, 128.29, 128.32, 128.38,
138.0, 138.3, 138.4, 138.6, 139.0; HRMS m/z calcd for
C62H70NO11 [M + NH4]+ 1004.4949, found 1004.4947.
22βꢀβ: foam; Rf = 0.6 (hexane/EtOAc = 6/4); [α]D23 −0.72 (c
0.74, CHCl3); IR (KBr) 2924, 1736, 1450, 1365, 1095, 1072, 741,
702 cm−1; 1H NMR (500 MHz, CDCl3) δ 3.11 (s, 3H), 3.31 (dd, J
= 9.8, 8.9 Hz, 1 H), 3.35–3.43 (m, 3 H), 3.50–3.62 (m, 4 H),
3.62–3.68 (m, 2 H), 3.81 (dd, J = 9.5, 8.9 Hz, 1 H), 3.89 (dd, J =
11.9, 8.5 Hz, 1 H), 4.00–4.09 (m, 3 H), 4.11 (d, J = 11.0 Hz, 1 H),
4.32 (d, J = 11.0 Hz, 1 H), 4.42 (d, J = 12.2 Hz, 1 H), 4.48 (d, J
21β: foam; Rf = 0.5 (hexane/EtOAc = 2/1), 0.32 (hexane/
CHCl3/acetone = 20/20/1, 2 times); [α]D23 +13 (c 1.1, CHCl3); IR
1
(KBr) 2908, 1458, 1365, 1095, 1049, 741, 702 cm−1; H NMR