Oligosaccharide Library
FULL PAPER
1HNMR (400 MHz, CDCl 3): d = 0.05 (s, 3H), 0.06 (s, 3H), 0.88 (s, 9H),
1.90 (s, 3H), 2.01 (s, 3H), 2.02 (s, 3H), 2.03 (s, 3H), 2.04 (s, 3H), 2.05 (s,
3H), 2.09 (s, 3H), 3.25–3.30 (m, 1H), 3.40 (s, 1H, OH), 3.52 (distorted t,
J=9.2 Hz, 1H), 3.54–3.62 (m, 3H), 3.69 (dd, J=11.1, 5.4 Hz, 1H), 3.74–
3.82 (m, 1H), 3.81 (dd, J=11.1, 5.3 Hz, 1H), 3.96 (dd, J=11.4, 2.2 Hz,
1H), 4.08 (dd, J=11.2, 1.5 Hz, 1H), 4.19 (dd, J=12.4, 2.8 Hz, 1H), 4.23
(dd, J=12.3, 4.8 Hz, 1H), 4.47 (d, J=8.2 Hz, 1H), 4.51 (d, J=11.4 Hz,
1H), 4.55 (d, J=11.4 Hz, 1H), 4.58 (d, J=8.1 Hz, 1H), 4.83–4.91 (m,
2H), 4.95 (brdt, J=7.6, 2.0 Hz, 1H), 5.04 (dd, J=9.6, 8.1 Hz, 1H), 5.07
(t, J=9.7 Hz, 1H), 5.189 (brt, J=8.2 Hz, 1H), 5.194 (t, J=8.6, 1H),
7.19–7.24 (m, 2H), 7.27–7.37 (m, 6H), 7.56–7.62 (m, 2H); 13C NMR
(KBr): n˜
=
1755 (s), 1375 (m), 1238 (s), 1156, 1048 (s), 837, 743,
700 cmꢀ1; HRMS (FAB): m/z: calcd for C68H90O29SeNaSi: 1501.4400;
found 1501.4414 [M+Na]+.
Tetrasaccharide 30 f: Glycosyl donor 13 f (62.2 mg, 0.10 mmol) and glyco-
syl acceptor 26d (51.2 mg, 0.050 mmol); product 30 f (41.9 mg, 57%).
1HNMR (400 MHz, CDCl 3): d = 0.06 (s, 3H), 0.08 (s, 3H), 0.90 (s, 9H),
1.88, (s, 3H), 1.89 (s, 3H), 1.92 (s, 3H), 1.97 (s, 3H), 1.97 (s, 3H), 2.00 (s,
3H), 2.00 (s, 3H), 2.05 (s, 3H), 2.08, (s, 3H), 3.28 (brdt, J=9.7, 2.7 Hz,
1H), 3.35 (brd, J=0.8 Hz, 1H, OH), 3.40 (distorted t, J=10.7 Hz, 1H),
3.40–3.46 (m, 1H), 3.49 (distorted ddd, J=9.9, 5.3, 1.3 Hz, 1H), 3.56 (t,
J=8.6 Hz, 1H), 3.61 (t, J=9.5 Hz, 1H),3.67 (dd, J=29.5, 5.7 Hz, 1H),
3.67 (t, J=5.8 Hz, 1H), 3.71–3.77 (m, 1H), 3.74 (t, J=9.5 Hz, 1H), 3.83–
3.88 (m, 2H), 4.01 (brdd, J=11.3, 1.3 Hz, 1H), 4.10–4.19 (m, 2H), 4.19
(brdd, J=10.1, 1.1 Hz, 1H), 4.53–4.57 (m, 2H), 4.65 (d, J=11.4 Hz, 1H),
4.71 (d, J=10.3 Hz, 1H), 4.85 (dd, J=9.5, 8.1 Hz, 1H), (dd, J=9.5,
8.1 Hz, 1H), 4.91 (dd, J=10.2, 9.1 Hz, 1H), 4.96 (dd, J=9.7, 8.2 Hz, 1H),
5.01 (t, J=9.7 Hz, 1H), 5.147 (t, J=9.6 Hz, 2H), 5.152 (t, J=9.5 Hz,
1H), 5.20 (t, J=9.5 Hz, 1H), 7.20–7.34 (m, 13H), 7.51–7.54 (m, 2H);
13C NMR (100 MHz, CDCl3): d = ꢀ5.35 (CH3), ꢀ4.93 (CH3), 18.36 (C),
20.34 (CH3), 20.53 (CH3, 2C), 20.66 (CH3, 2C), 20.81 (CH3, 2C), 20.82
(CH3), 21.08 (CH3), 25.95 (CH3, 3C), 61.58 (CH2), 61.68 (CH2), 67.73
(CH2), 68.24 (CH), 68.31 (CH), 69.14 (CH2), 70.72 (CH), 71.47 (CH),
71.99 (CH), 72.05 (CH), 72.08 (CH), 72.63 (CH), 74.65 (CH2), 74.69
(CH2), 74.91 (CH), 75.02 (CH), 75.07 (CH), 75.37 (CH), 75.88 (CH),
76.17 (CH), 80.62 (CH), 81.77 (CH), 85.50 (CH), 100.78 (CH), 100.88
(CH), 101.07 (CH), 127.79 (CH, 2C), 127.85 (CH), 127.93 (CH, 2C),
128.01 (CH), 128.11 (CH), 128.25 (C), 128.46 (CH, 2C), 128.53 (CH,
2C), 129.18 (CH, 2C), 134.10 (CH, 2C), 137.53 b(C), 138.02 (C), 169.05
(C=O), 169.24 (C=O, 2C), 169.65 (C=O), 169.81 (C=O), 170.07 (C=O),
170.23 (C=O), 170.25 (C=O), 170.53 (C=O); IR (KBr): n˜ = 3495, 1755
(s), 1374 (m), 1242 (s), 1223 (s), 1049 (s), 835, 743, 698 cmꢀ1; HRMS
(FAB): m/z: calcd for C68H91O29SeSi: 1479.4581; found 1479.4619
[M+H]+.
(100 MHz, CDCl3): d
=
ꢀ5.21 (CH3), ꢀ5.18 (CH3), 18.43 (C), 20.39
(CH3), 20.56 (CH3, 2C), 20.62 (CH3), 20.77 (CH3), 20.82 (CH3), 21.01
(CH3), 25.95 (CH3, 3C), 61.68 (CH2), 62.68 (CH2), 67.51 (CH2), 68.34
(CH), 68.40 (CH), 70.79 (CH), 71.44 (CH), 71.95 (CH), 71.99 (CH),
72.62 (CH), 74.64 (CH), 75.85 (CH2), 76.02 (CH), 76.60 (CH), 79.77
(CH), 81.14 (CH), 85.27 (CH), 100.65 (CH), 101.08 (CH), 127.63 (C),
127.73 (CH, 2C), 127.98 (CH), 128.23 (CH), 128.51 (CH, 2C), 129.10
(CH, 2C), 134.78 (CH, 2C), 137.50 (C), 168.94 (C=O), 169.27 (C=O),
169.34 (C=O), 169.57 (C=O), 169.99 (C=O), 170.28 (C=O), 170.59 (C=
O); IR (KBr): n˜ = 3504, 1755, 1375, 1235, 1048 cmꢀ1; HRMS (FAB): m/
z: calcd for C56H81O30SeSi: 1143.3372; found 1143.3381 [M+H]+.
Tetrasaccharide 28 f: Glycosyl donor 23 f (322 mg, 0.40 mmol) and glyco-
syl acceptor 23d (138 mg, 0.20 mmol); product 28 f (199 mg, 74%).
1HNMR (400 MHz, CDCl 3): d = 0.06 (s, 6H), 0.88 (s, 9H), 2.00 (s, 3H),
2.00 (s, 3H), 2.03 (s, 6H), 2.03 (s, 6H), 2.04 (s, 3H), 2.07 (s, 3H), 2.09 (s,
3H), 2.11 (s, 3H), 3.28 (brddd, J=7.7, 5.3, 2.0 Hz, 1H), 3.32 (brs, 1H,
OH), 3.39 (t, J=9.2 Hz, 1H), 3.40 (brs, 1H, OH), 3.45–3.51 (m, 1H),
3.53 (t, J=9.9 Hz, 1H), 3.56 (t, J=9.6 Hz, 1H), 3.59 (t, J=8.9 Hz, 1H),
3.62 (dd, J=11.4, 6.8 Hz, 1H), 3.74–3.82 (m, 3H), 3.95 (dd, J=11.3,
2.1 Hz, 1H), 4.12–4.25 (m, 5H), 4.44 (d, J=8.2 Hz, 1H), 4.55 (d, J=
8.1 Hz, 1H), 4.59 (d, J=8.2 Hz, 1H), 4.73 (d, J=10.3 Hz, 1H), 4.91 (t,
J=8.7 Hz, 1H), 4.96 (t, J=10.0 Hz, 1H), 4.98–5.09 (m, 4H), 5.18 (t, J=
9.5 Hz, 1H), 5.19 (t, J=9.5 Hz, 1H), 7.28–7.32 (m, 3H), 7.53–7.58 (m,
2H); 13C NMR (100 MHz, CDCl3): d = ꢀ5.27 (CH3), ꢀ5.19 (CH3), 18.45
(C), 20.35 (CH3), 20.40 (CH3), 20.54 (CH3, 2C), 20.56 (CH3, 2C), 20.62
(CH3), 20.64 (CH3), 20.94 (CH3), 21.10 (CH3), 25.96 (CH3, 3C), 61.65
(CH2), 61.69 (CH2), 62.79 (CH2), 68.33 (CH), 68.35 (CH), 68.39 (CH),
68.57 (CH), 68.91 (CH2), 70.67 (CH), 70.80 (CH), 71.52 (CH), 71.94
(CH), 72.01 (CH), 72.09 (CH), 72.57 (CH), 72.65 (CH), 76.51 (CH),
80.54 (CH), 81.82 (CH), 85.25 (CH), 85.74 (CH), 100.96 (CH), 101.10
(CH), 101.20 (CH), 128.01 (C), 128.38 (CH), 129.15 (CH), 134.16 (CH),
169.06 (C=O, 2C), 169.29 (C=O), 169.39 (C=O, 3C), 170.23 (C=O),
170.25 (C=O), 170.53 (C=O), 170.59 (C=O); IR (KBr): n˜ = 3501, 2957,
1755 (s), 1375, 1231 (s), 1169, 1063 (m), 1040 (m), 837 cmꢀ1; HRMS
(FAB): m/z: calcd for C56H81O30SeSi: 1341.3747; found 1341.3763
[M+H]+.
Pentasaccharide 31 f: Glycosyl donor 26 f (57.1 mg, 0.050 mmol) and gly-
cosyl acceptor 23d (41.5 mg, 0.06 mmol); product 31 f (31.0 mg, 37%).
1HNMR (400 MHz, CDCl 3): d = 0.08 (s, 3H), 0.09 (s, 3H), 0.92 (s, 9H),
1.90 (s, 3H), 1.995 (s, 3H), 1.999 (s, 3H), 2.002 (s, 3H), 2.02 (s, 3H), 2.03
(s, 3H), 2.06 (s, 3H), 2.09 (s, 3H), 3.32 (brdt, J=9.6, 2.4 Hz, 1H), 3.36–
3.89 (m, 17H; containing 2 OH), 4.12–4.24 (m, 4H), 4.41 (d, J=8.1 Hz,
1H), 4.55–4.62 (m, 4H), 4.66 (d, J=11.5 Hz, 1H), 4.73 (d, J=10.3 Hz,
1H), 4.83 (dd, J=9.7, 7.9 Hz, 1H), 4.87–5.09 (m, 7H), 5.14–5.22 (m, 3H),
7.23–7.35 (m, 8H), 7.52–7.56 (m, 2H); 13C NMR (100 MHz, CDCl3): d =
ꢀ5.40 (CH3), ꢀ4.94 (CH3), 18.36 (C), 20.34 (CH3, 2C), 20.52 (CH3, 4C),
20.63 (CH3), 20.65 (CH3), 20.78 (CH3), 20.82 (CH3), 20.85 (CH3), 21.06
(CH3), 25.94 (CH3, 3C), 61.68 (CH2, 3C), 68.30 (CH2), 68.35 (CH, 3C),
68.68 (CH), 69.14 (CH2), 70.72 (CH, 2C), 71.53 (CH), 71.97 (CH, 2C),
72.20 (CH), 72.56 (CH), 72.64 (CH), 74.62 (CH2), 74.88 (CH), 75.46
(CH), 75.72 (CH), 75.77 (CH), 77.55 (CH), 80.42 (CH), 81.84 (CH),
85.05 (CH), 85.37 (CH), 100.80 (CH), 101.01 (CH), 101.07 (CH), 101.29
(CH), 121.45 (C), 127.82 (CH), 127.92 (CH, 2C), 127.98 (CH), 128.44
(CH, 2C), 129.16 (CH, 2C), 134.02 (CH, 2C), 138.04 (C), 168.94 (C=O),
169.04 (C=O), 169.27 (C=O, 3C), 169.30 (C=O), 169.81 (C=O), 170.16
(C=O), 170.21 (C=O), 170.22 (C=O), 170.52 (C=O), 170.56 (C=O);
HRMS (FAB): m/z: calcd for C75H100O37SeNaSi: 1699.4776; found
1699.4816 [M+Na]+.
Tetrasaccharide 29 f: Glycosyl donor 26 f (133 mg, 0.11 mmol) and glyco-
syl acceptor 13d (57.5 mg, 0.11 mmol); product 29 f (45.5 mg, 28%) and
29d (46.5 mg, 31%). Compound 29d could be transformed quantitatively
to 29 f by standard silylation conditions. 1HNMR (400 MHz, CDCl 3): d
= 0.04 (s, 3H), 0.05 (s, 3H), 0.89 (s, 9H), 1.87 (s, 3H), 1.88 (s, 3H), 1.95
(s, 3H), 1.98 (s, 3H), 1.995 (s, 3H), 1.996 (s, 3H), 2.01 (s, 3H), 2.02 (s,
3H), 2.07 (s, 3H), 3.34–3.59 (m, 6 H + OH), 3.63–3.81 (m, 4H), 3.81–
3.86 (m, 2H), 4.05–4.16 (m, 2H), 4.16–4.21 (m, 2H), 4.43 (d, J=8.1 Hz,
1H), 4.47–4.66 (m, 7H), 4.79–4.93 (m, 3H), 4.99 (dd, J=9.6, 8.1 Hz, 1H),
5.04 (t, J=9.7 Hz, 1H), 5.14–5.22 (m, 3H), 7.18–7.32 (m, 13H), 7.57 (dd,
Pentasaccharide 32 f: Glycosyl donor 23 f (80.6 mg, 0.10 mmol) and gly-
cosyl acceptor 26d (51.4 mg, 0.050 mmol); product 32 f (26.8 mg, 32%)
and 32d (20.3 mg, 26%). 1HNMR (400 MHz, CDCl 3): d = 0.05 (s, 3H),
0.06 (s, 3H), 0.88 (s, 9H), 1.91 (s, 3H), 1.93 (s, 3H), 1.99 (s, 3H), 2.01 (s,
3H), 2.03 (s, 9H), 2.04 (s, 3H), 2.05 (s, 3H), 2.09 (s, 6H), 2.12 (s, 3H),
3.27 (ddd, J=8.6, 5.8, 2.6 Hz, 1H), 3.33 (brs, 1H, OH), 3.40 (brt, J=
9.0 Hz, 1H), 3.43 (brs, 1H, OH), 3.47–3.61 (m, 6H), 3.61–3.69 (m, 2H),
3.74–3.86 (m, 2H), 3.95 (dd, J=11.2, 2.0 Hz, 1H), 4.05 (brd, J=10.0 Hz,
1H), 4.12–4.26 (m, 5H), 4.45 (d, J=8.0 Hz, 1H), 4.50–4.60 (m, 4H), 4.75
(d, J=10.4 Hz, 1H), 4.87 (dd, J=9.6, 8.0 Hz, 1H), 4.93 (dd, J=10.0,
9.2 Hz, 1H), 4.95 (t, J=8.8 Hz, 1H), 4.99 (t, J=9.0 Hz, 1H), 5.01 (t, J=
8.4 Hz, 1H), 5.07 (t, J=9.6 Hz, 2H), 5.14–5.25 (m, 3H), 7.21–7.38 (m,
8H), 7.52–7.58 (m, 2H); 13C NMR (100 MHz, CDCl3): d = ꢀ5.25 (CH3),
J=7.9, 1.5 Hz, 2H); 13C NMR (100 MHz, CDCl3): d
=
ꢀ5.41 (CH3),
ꢀ4.97 (CH3), 18.34 (C), 20.31 (CH3), 20.52 (CH3, 2C), 20.63 (CH3), 20.74
(CH3), 20.78 (CH3, 2C), 20.92 (CH3), 25.93 (CH3, 3C), 61.63 (CH2), 61.74
(CH2), 67.04 (CH2), 68.35 (CH), 68.47 (CH2), 68.71 (CH), 70.70 (CH),
71.44 (CH), 71.96 (CH), 72.01 (CH), 72.14 (CH), 72.52 (CH), 74.59
(CH2), 74.67 (CH2), 74.85 (CH), 75.52 (CH), 75.70 (CH), 75.82 (CH),
75.88 (CH), 75.92 (CH), 79.62 (CH), 80.71 (CH), 85.09 (CH), 100.32
(CH), 101.07 (CH), 101.11 (CH), 127.22 (C), 127.66 (CH, 2C), 127.76
(CH), 127.80 (CH, 2C), 127.93 (CH), 128.33 (CH), 128.41 (CH, 2C),
128.50 (CH, 2C), 129.05 (CH, 2C), 135.06 (CH, 2C), 137.60 (C), 138.09
(C), 168.75 (C=O), 169.20 (C=O), 169.24 (C=O), 169.46 (C=O), 169.64
(C=O), 170.00 (C=O), 170.13 (C=O), 170.23 (C=O), 170.55 (C=O); IR
Chem. Eur. J. 2005, 11, 6159 – 6174
ꢀ 2005 Wiley-VCHVerlag GmbH& Co. KGaA, Weinheim
6169