K. Sato et al. / Tetrahedron Letters 44 (2003) 9331–9335
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8. Physical data for 9: [h]2D3=+59.0° (c=1.9, CHCl3) 1H
NMR (500 MHz, CDCl3): l 8.10–7.23 (20H, m, Ar-H),
6.25 (1H, s, NH), 6.00 (1H, d, H-4), 5.77 (1H, dd,
J=10.4 Hz, H-2), 5.63 (1H, dd, J=3.1 Hz, H-3), 4.87
(1H, d, J=7.9 Hz, H-1), 4.72 (2H, s, CH2CCl3), 4.67 (1H,
dd, H-6a), 4.45 (1H, dd, H-6b), 4.36 (1H, m, H-5), 3.98
and 3.76 (2H, m, OCH2 of sugar unit), 3.65 (2H, s,
NCH2CO), 3.55–3.49 (4H, m, NCH2 of sugar unit, NCH2
of b-alanine), 2.72 (2H, t, J=6.7 Hz, COCH2 of b-ala-
nine), 1.43 (9H, s, t-Bu). 13C NMR (125 MHz, CDCl3): l
169.3, 166.0, 165.5, 165.3, 133.7, 133.5, 133.4, 133.3,
130.0, 129.7, 129.3, 129.2, 129.0, 128.7, 128.6, 128.5,
128.3, 101.7, 94.8, 80.9, 74.1, 71.6, 71.5, 69.8, 68.9, 68.1,
62.1, 51.7, 44.9, 39.2, 33.0, 28.3. MALDI-TOFMS: calcd
for C48H49Cl3N2O15: 998, found 1021[M+Na]+.
(1H, dd, J2,3=10.4 Hz, H-2), 5.65 (1H, dd, J3,4=3.6 Hz,
H-2), 4.84 (1H, d, J1,2=7.9 Hz, H-1), 4.74 (2H, s,
CH2CCl3), 4.68 (1H, dd, H-6a), 4.44 (1H, dd, H-6b), 4.36
(1H, t, H-5), 4.01, 3.70 (2H, m, OCH2 of sugar unit), 3.85
(2H, s, COCH2N), 3.60 (2H, t, NCH2 of b-alanine),
3.57-3.34 (4H, m, NCH2 of sugar unit, NCH2 of b-ala-
nine), 2.78 (2H, t, CH2CO), 2.11 and 1.99 (2H, m,
CH2CO), 1.44 (9H, s, t-Bu). 13C-NMR (125 MHz,
CDCl3): l 171.4, 169.1, 166.0, 165.5, 165.4, 133.4, 130.0,
129.7, 129.7, 129.3, 128.9, 128.7, 128.5, 128.3, 101.6, 94.8,
81.0, 74.0, 71.6, 71.3, 69.9, 68.9, 68.0, 62.0, 52.0, 44.8,
39.0, 35.2, 34.7, 33.2, 28.2. HR-FABMS: calcd for
C51H54Cl3N3O16: 1069.2570, found 1070.2609[M+H]+.
1
Physical data 18 [h]D23=+53.5° (c=1.8, CHCl3) H NMR
(500 MHz, CDCl3): l 8.10–7.23 (20H, m, Ar-H), 6.69
(1H, s, NH), 6.10 (1H, s, NH), 6.01 (1H, d, H-4), 5.77
(1H, dd, H-2), 5.65 (1H, dd, H-3), 4.86 (1H, d, H-1), 4.73
(2H, s, CH2CCl3), 4.69 (1H, dd, H-6a), 4.44 (1H, m,
H-6b), 4.37 (1H, t, H-5), 4.01 and 3.72 (2H, OCH2 of
sugar unit), 3.85 (2H, s, COCH2N), 3.62 (2H, t, NCH2 of
b-alanine), 3.56-3.34 (2H, m, NCH2 of sugar unit), 3.18
(2H, m, NCH2 of GABA), 2.77 (2H, t, CH2CO of
b-alanine), 2.01–1.85 (2H, m, CH2CO of GABA), 1.67
(2H, m, CCH2C), 1.44 (9H, s, t-Bu). 13C NMR (125
MHz, CDCl3): l 172.6, 169.5, 166.0, 165.5, 165.4, 133.64,
133.61, 133.3, 120.0, 129.7, 129.3, 129.04, 128.95, 128.64,
128.61, 128.5, 128.3, 101.6, 94.7, 81.0, 74.1, 71.5, 71.4,
69.9, 69.0, 68.1, 62.0, 52.1, 44.9, 39.1, 39.0, 33.3, 28.3,
24.8. HR-FABMS: calcd for C52H56Cl3N3O16: 1083.2726,
found 1084.2780[M+H]+.
9. Physical data for 16 [h] 2D3=+57.5° (c=1.9, CHCl3) 1H
NMR (500 MHz, CDCl3): l 8.10–7.23 (20H, m, Ar-H),
6.42 (1H, s, NH), 6.01 (1H, s, NH), 6.00 (1H, d, H-4),
5.75 (1H, dd, J2,3=10.4 Hz, H-2), 5.64 (1H, dd, J3,4=3.1
Hz, H-3), 4.84 (1H, d, J1,2=7.9 Hz, H-1), 4.71 (2H, s,
CH2CCl3), 4.69 (1H, dd, H-6a), 4.44 (1H, dd, H-6b), 4.36
(1H, t, H-5), 3.99, 3.75 (2H, m, CH2O of sugar unit), 3.89
(2H, s, NCH2CO), 3.68–3.40 (6H, m, NHCH2CO,
NCH2C, CONHCH2), 2.79 (2H, t, COCH2C), 1.46 (9H,
s, t-Bu). 13C NMR (125 MHz, CDCl3): l 169.5, 166.1,
165.5, 165.5, 133.7, 133.4, 130.0, 129.7, 129.7, 129.3,
129.0, 128.7, 128.5, 128.3, 101.6, 94.7, 81.3, 74.1, 71.6,
71.4, 70.0, 68.6, 68.1, 52.3, 45.0, 42.5, 39.2, 33.4, 28.3.
HR-FABMS: calcd for C50H52Cl3N3O16: 1055.2413,
found 1056.2516[M+H]+.
1
Physical data 17 [h]D23=+53.0° (c=1.8, CHCl3) H NMR
10. MALDI-TOFMS of final compound 1: calcd for
(500 MHz, CDCl3): l 8.10–7.23 (20H, m, Ar-H), 6.79
(1H, s, NH), 6.00 (1H, d, H-4), 5.96 (1H, s, NH), 5.76
C83H134N14O44: 2063, found: 2086 [M+Na]+.