7780
J. Liu et al. / Bioorg. Med. Chem. 15 (2007) 7773–7788
J = 7.3 Hz, 1H), 5.33 (s, 2H), 4.93 (t, J = 5.2 Hz, 1H),
4.41 (t, J = 5.2 Hz, 1H), 4.26 (dd, J = 10.0 Hz,
J = 4.5 Hz, 1H), 4.09 (dd, J = 10.0 Hz, J = 3.8 Hz,
1H), 2.91 (d, J = 6.2 Hz, 2H), 2.83 (d, J = 5.1 Hz, 2H),
3200, 3006, 2950, 2842, 1730, 1647, 1600, 1456, 1395,
1
1370, 1060, 900 cmꢀ1; H NMR (BHSC-500, DMSO-
d6): d = 9.95 (s, 1H), 8.04 (s, 1H), 7.37 (t, J = 7.4 Hz,
1H), 7.23 (t, J = 7.6 Hz, 1H), 7.16 (d, J = 7.4 Hz, 2H),
7.14 (t, J = 7.1 Hz, 2H), 7.12 (d, J = 7.1 Hz, 2H), 7.09
(t, J = 7.1 Hz, 1H), 7.05 (d, J = 7.4 Hz, 1H), 6.93 (d,
J = 7.6 Hz, 1H), 6.90 (d, J = 7.4 Hz, 2H), 5.40 (s, 2H),
4.99 (s, 1H), 4.91 (d, J = 5.5 Hz, 1H), 4.82 (t,
J = 5.7 Hz, 1H), 4.26 (m, J = 5.3 Hz, 2 H), 3.17 (d,
J = 5.3 Hz, 2H), 2.95 (d, J = 5.1 Hz, 2H), 1.47 (s, 9H).
Anal. Calcd for C33H35N3O6 C 69.58, H 6.19, N 7.38.
Found C 69.41, H 6.10, N 7.53.
1.53 (s, 9H), 1.34 (m, J = 5.1 Hz, 1H), 1.07 (d,
20
D
J = 5.3 Hz, 6H). ½aꢁ ꢀ33 ꢁ (c 0.31, CHCl3–CH3OH,
1:1, v/v); Anal. Calcd for C30H37N3O5 C 69.34, H
7.18, N 8.09. Found C 69.25, H 7.08, N 8.26.
4.1.6. N-[(3S)-N-Boc-1,2,3,4-tetrahydro-b-carboline-3-
carbonyl]-L-alanine bensylester (3d). Yield: 95%. Mp
110–112 ꢁC; ESI/MS (m/z) 478 [M+H]+. IR (KBr):
3447, 3342, 3001, 2945, 2842, 1761, 1733, 1602, 1455,
1391, 1373, 1062, 899 cmꢀ1
;
1H NMR (BHSC-500,
4.1.10. N-[(3S)-N-Boc-1,2,3,4-tetrahydro-b-carboline-3-
carbonyl]-L-tryptophan benzylester (3h). Yield: 92%.
Mp 136–138 ꢁC; ESI/MS (m/z) 593 [M+H]+. IR (KBr):
3444, 3337, 3208, 3005, 2945, 2835, 1758, 1736, 1645,
DMSO-d6): d = 9.93 (s, 1H), 8.04 (s, 1H), 7.30 (t,
J = 7.3 Hz, 1H), 7.24 (t, J = 7.3 Hz, 1H), 7.22 (t,
J = 7.2 Hz, 2H), 7.14 (d, J = 7.2 Hz, 2H), 7.11 (t,
J = 7.2 Hz, 1H), 6.95 (d, J = 7.3 Hz, 1H), 6.83 (d,
J = 7.3 Hz, 1H), 5.35 (s, 2H), 4.86 (d, J = 5.4 Hz, 1H),
4.56 (m, J = 5.2 Hz, 1H), 4.22 (dd, J = 10.1 Hz,
J = 4.5 Hz, 1H), 4.15 (dd, J = 10.0 Hz, J = 3.7 Hz,
1602, 1449, 1390, 1370, 1067, 903 cmꢀ1 1H NMR
;
(BHSC-500, DMSO-d6): d = 9.96 (s, 1H), 9.89 (s, 1H),
8.03 (s, 1 H), 7.29 (t, J = 7.3 Hz, 1H), 7.27 (t,
J = 7.2 Hz, 1H), 7.22 (t, J = 7.0 Hz, 2H), 7.14 (d,
J = 7.0 Hz, 2H), 7.12 (d, J = 7.5 Hz, 1H), 7.11 (t,
J = 7.0 Hz, 1H), 7.10 (t, J = 7.5 Hz, 1H), 7.09 (d,
J = 7.3 Hz, 1H), 7.07 (t, J = 7.5 Hz, 1H), 7.02 (d,
J = 7.3 Hz, 1H), 6.97 (d, J = 7.2 Hz, 1H), 6.85 (s, 1H),
5.36 (s, 2H), 4.96 (d, J = 5.2 Hz, 1H), 4.73 (t,
J = 5.1 Hz, 1H), 4.27 (d, J = 5.0 Hz, 2H), 3.17 (d,
1H), 2.92 (d, J = 10.0 Hz, 2H), 1.57 (d, J = 5.0 Hz,
20
D
3H), 1.46 (s, 9H). ½aꢁ ꢀ100 ꢁ (c 0.38, CHCl3–CH3OH,
1:1, v/v); Anal. Calcd for C27H31N3O5 C 67.91, H,
6.54, N 8.80. Found C 67.72, H 6.40, N 8.90.
4.1.7. N-[(3S)-N-Boc-1,2,3,4-tetrahydro-b-carboline-3-
carbonyl]-L-glycine benzylester (3e). Yield: 95%. Mp
139–141 ꢁC; ESI/MS (m/z) 464 [M+H]+. IR (KBr):
3444, 3336, 3004, 2940, 2845, 1761, 1730, 1602, 1455,
J = 5.2 Hz, 2H), 2.97 (d, J = 6.2 Hz, 2H), 1.47 (s, 9H).
20
D
½aꢁ ꢀ77 ꢁ (c 0.36, CHCl3–CH3OH, 1:1, v/v); Anal.
Calcd for C35H36N4O5 C 70.93, H 6.12, N 9.45. Found
C 70.80, H 6.01, N 9.60.
1392, 1375, 1060, 903 cmꢀ1 1H NMR (BHSC-500,
;
DMSO-d6): d = 9.96 (s, 1H), 8.05 (s, 1H), 7.27 (t,
J = 7.4 Hz, 1H), 7.23 (t, J = 7.2 Hz, 2H), 7.18 (t,
J = 7.4 Hz, 1H), 7.15 (d, J = 7.2 Hz, 2H), 7.11 (t,
J = 7.2 Hz, 1H), 6.93 (d, J = 7.4 Hz, 1H), 6.85 (d,
J = 7.4 Hz, 1H), 5.36 (s, 2H), 4.86 (d, J = 5.2 Hz, 1H),
4.25 (dd, J = 10.0 Hz, J = 4.3 Hz, 1H), 4.17 (dd,
4.1.11.
N-(N-Boc-3S-1,2,3,4-tetrahydro-b-carboline-3-
carbonyl)-L-aspartic acid dibenzylester (3i). Yield: 92%.
Mp 132–134ꢁC; ESI/MS (m/z) 612 [M+H]+; IR (KBr):
3445, 3340, 3214, 3002, 2952, 2843, 1758, 1730, 1646,
1602, 1455, 1388, 1369, 1064, 901 cmꢀ1 1H NMR
;
J = 10.0 Hz, J = 3.4 Hz, 1H), 4.15 (s, 2H), 2.93 (d,
(BHSC-500, DMSO-d6): d = 10.01 (s, 1H), 8.02 (s,
1H), 7.30 (t, J = 7.2 Hz, 1H), 7.24 (t, J = 7.2 Hz, 1H),
7.22 (t, J = 7.0 Hz, 2H), 7.20 (t, J = 7.0 Hz, 2H), 7.15
(d, J = 7.0 Hz, 2H), 7.13 (d, J = 7.0 Hz, 2H), 7.11 (t,
J = 7.0 Hz, 1H), 7.10 (t, J = 7.0 Hz, 1H), 7.02 (d,
J = 7.2 Hz, 1H), 6.98 (d, J = 7.2 Hz, 1H), 5.36 (s, 2H),
5.34 (s, 2H), 4.94 (d, J = 5.2 Hz, 1H), 4.79 (t,
J = 5.2 Hz, 1H), 4.27 (d, J = 5.2 Hz, 2H), 2.94 (d,
J = 5.0 Hz, 2H), 2.87 (d, J = 5.2 Hz, 2H), 1.47 (s, 9H).
Anal. Calcd for C35H37N3O7 C 68.72, H 6.10, N 6.87.
Found C 68.54, H 6.19, N 7.00.
20
D
J = 10.0 Hz, 2H), 1.48 (s, 9H). ½aꢁ ꢀ84 ꢁ (c 0.36,
CHCl3–CH3OH, 1:1, v/v); Anal. Calcd for C26H29N3O5
C 67.37, H, 6.31, N 9.07. Found C 67.25, H 6.18, N 9.19.
4.1.8. N-[(3S)-N-Boc-1,2,3,4-tetrahydro-b-carboline-3-
carbonyl]-L-phenylalanine benzylester (3f). Yield: 96%.
Mp 144–146 ꢁC; ESI/MS (m/z) 554 [M+H]+. IR (KBr):
3442, 3350, 3202, 3009, 2944, 2842, 1758, 1734, 1642,
1601, 1455, 1390, 1371, 1065, 902 cmꢀ1 1H NMR
;
(BHSC-500, DMSO-d6): d = 9.95 (s, 1H), 7.99 (s, 1H),
7.28 (t, J = 7.3 Hz, 1H), 7.25 (t, J = 7.6 Hz, 2H), 7.22 (t,
J = 7.3 Hz, 2H),7.17 (t, J = 7.3 Hz, 1H), 7.15 (d,
J = 7.4 Hz, 2H), 7.13 (d, J = 7.3 Hz, 2H), 7.11 (t,
J = 7.3 Hz, 1H), 7.03 (t, J = 7.3 Hz, 1H), 6.98 (d,
J = 7.6 Hz, 1H), 6.82 (d, J = 7.2 Hz, 1H), 5.34 (s, 2H),
4.95 (d, J = 5.2 Hz, 1H), 4.84 (t, J = 5.2 Hz, 1H), 4.25
(dd, J = 10.0 Hz, J = 4.1 Hz, 1H), 4.15 (dd, J = 10.0 Hz,
4.1.12.
N-(N-Boc-3S-1,2,3,4-tetrahydro-b-carboline-3-
carbonyl)-L-glutamic acid dibenzylester (3j). Yield: 90%.
Mp 144–146ꢁC; ESI/MS (m/z) 626 [M+H]+; IR (KBr):
3445, 3204, 3007, 2948, 2826, 1735, 1640, 1600, 1452,
1391, 1375, 1062, 900 cmꢀ1 1H NMR (BHSC-500,
;
DMSO-d6): d = 9.92 (s, 1H), 8.03 (s, 1H), 7.36 (t,
J = 7.5 Hz, 1H), 7.27 (t, J = 7.5 Hz, 1H), 7.24 (t,
J = 7.3 Hz, 2H), 7.22 (t, J = 7.4 Hz, 2H), 7.21 (d,
J = 7.3 Hz, 2H), 7.19 (d, J = 7.4 Hz, 2H), 7.16 (t,
J = 7.3 Hz, 1H), 7.14 (t, J = 7.4 Hz, 1H), 7.04 (d,
J = 7.5 Hz, 1H), 6.86 (d, J = 7.5 Hz, 1H), 5.36 (s, 2H),
5.33 (s, 2H), 4.93 (d, J = 5.3 Hz, 1H), 4.46 (t,
J = 5.5 Hz, 1H), 4.25 (d, J = 5.4 Hz, 2H), 2.95 (d,
J = 5.2 Hz, 2 H), 2.25 (t, J = 5.5 Hz, 2H), 2.22 (t,
J = 3.5 Hz, 1H), 3.19 (d, J = 5.2 Hz, 2H), 2.92 (d,
20
D
J = 10.0 Hz, 2H), 1.49 (s, 9H). ½aꢁ ꢀ52 ꢁ (c 0.38,
CHCl3–CH3OH, 1:1, v/v); Anal. Calcd for C33H35N3O5C
71.59, H 6.37, N 7.59. Found C 71.74, H 6.22, N 7.77.
4.1.9. N-(N-Boc-3S-1,2,3,4-tetrahydro-b-carboline-3-car-
bonyl)-L-tyrosine benzylester (3g). Yield: 90%. Mp 155–
157 ꢁC; ESI/MS (m/z) 570 [M+H]+; IR (KBr): 3444,