P. Kopczacki et al. /Phytochemistry 58 (2001) 775–787
781
(t, C-1), 40.7 (d, C-2), 45.9 (d, C-9), 47.3 (t, C-10), 71.0
(s, C-3), 71.4 (t, C-13), 75.0 (d, C-8), 79.4 (d, C-30), 83,1
(d, C-20), 126.5 (d, C-Ph), 126.7 (s, C-Ph), 128.2 (d, C-
Ph), 128.5 (d, C-Ph), 128.7 (d, C-Ph), 128.9 (d, C-Ph),
132.1 (d, C-Ph), 140.9 (s, C-Ph), 164.2 (s, NCO), 170.1
(s, C-10), 175.1 (s, C-4); LSIMS m/z (rel. int.): 516
[M+H]+ (38), 498 (15), 460 (4), 307 (29), 268 (29), 231
(6), 222 (6), 154 (100); HR LSIMS m/z: [M+H]+ calc.
for C31H34O6N: 516.23859, found: 516.23813.
Ph), 135.7 (s, C-2), 135.7 (s, C-Ph), 137.8 (d, C-13),
141.1 (s, C-Ph), 141.8 (d, C-5), 164.1 (s, NCO), 170.1 (s,
C-10); EIMS 70 eV, m/z (rel. int.): 481 [M]+ (6), 268
(100), 223 (8), 222 (42), 215 (14), 214 (72), 199 (41), 193
(33), 158 (28), 145 (5), 143 (7), 119 (10), 105 (23), 91
(17), 77 (8); HR EIMS m/z: [M]+ calc. for C31H31O4N:
481.22531, found: 481.22887.
4.4.5. Compound 20
TLC Rf=0.63 (C6H6–Me2CO 8:2); mp 58–63 ꢀC;
[a]2D0=À31.38ꢀ (CHCl3, c 1.0); UV lmax (EtOH) nm: 242
(" 24950); IR ꢁmax (KBr) cmÀ1: 3439, 3063, 2952, 2869,
4.4.3. Compound 14
TLC Rf=0.25 (hexane–EtOAc 8:2); mp 86–91 ꢀC;
[a]2D0=+35.24ꢀ (CHCl3, c 1.0); UV lmax (EtOH) nm:
243 (" 16937); IR ꢁmax (CHCl3) cmÀ1: 3555, 3434, 2957,
1
1758, 1655; H NMR: d 1.09 (3H, s, H-15), 1.15 (3H, s,
H-14), 1.29 (3H, s, H-12), 1.58–1.59 (2H, m, H-10), 1.63
(2H, dd, J1a,1b=13.5 Hz and J=5.9 Hz, H-1), 2.35–2.41
(1H, m, H-2a), 2.49–2.55 (1H, m, 9a), 2.56 (1H, d,
1
1772, 1746,1655; H NMR: ꢀ 0.67 (3H, s, H-15), 0.85
(3H, s, H-14), 0.95 (1H, t, J10b,10a=11.8 Hz, H-10b),
1.18 (1H, d, J5b,5a=6.3 Hz, H-5b), 1.30–1.42 (3H, m, H-
1a, H-1b and H-10a), 1.60 (3H, s, H-12), 1.61 (1H, d,
J
4b,4a=15.0 Hz, H-4b), 2.82 (1H, d, J4a,4b=15.0 Hz, H-
0
0
0
4a), 5.00 (1H, d, J2 ,3 =6.2 Hz, H-2 ), 5.52 (1H, d,
0
0
0
J
5a,5b=6.3 Hz, H-5a), 1.99–2.05 (1H, m, H-2a), 2.25-
J3 ,2 =6.2 Hz, H-3 ), 6.06 (1H, d, J8b,9a=10.8 Hz, H-
8b), 7.13 (1H, br s, H-5), 7.24 (1H, br s, H-13), 7.28–7.57
(8H, m, H-Ph), 8.08–8.13 (2H, m, H-Ph); 13C NMR: ꢀ
30.6 (q, C-12), 31.8 (q, C-14), 32.1 (q, C-15), 32.5 (t, C-
4), 35.3 (s, C-11), 42.6 (t, C-1), 43.6 (t, C-10), 44.8 (d, C-
9), 53.9 (d, C-2), 70.7 (d, C-8), 71.3 (s, C-3), 74.7 (d, C-
30), 83,1 (d, C-20), 118.1 (s, C-6), 125.1 (s, C-7), 126.4 (d,
C-Ph), 126.6 (s, C-Ph), 128.1 (d, C-Ph), 128.5 (d, C-Ph),
128.7 (d, C-Ph), 128.9 (d, C-Ph), 132.0 (d, C-Ph), 138.9
(d, C-5), 140.9 (s, C-Ph), 141.9 (d, C-13), 164.1 (s,
NCO), 169.1 (s, C-10); EIMS 70 eV, m/z (rel. int.): 499
[M]+ (3), 481 (6), 464 (7), 446 (5), 268 (16), 232 (32), 223
(16), 222 (100), 217 (14), 199 (7), 193 (58), 189 (13), 165
(6), 145 (2), 137 (3), 119 (4), 105 (15), 91 (9), 77 (6), 43
(4); HR LSIMS m/z: [M+H]+ calc. for C31H34O5N:
500.24371, found: 500.24270.
2.32 (1H, m, H-9a), 4.08 (1H, d, J13b,13a=9.4 Hz, H-
13b), 4.21 (1H, d, J13a,13b=9.4 Hz, H-13a), 5.02 (1H, 0d,
0
0
0
0
0
J2 ,3 =5.9 Hz, H-2 ), 5.56 (1H, d, J3 ,2 =5.9 Hz, H-3 ),
5.83 (1H, d, J8a,9a=4.5 Hz, H-8a), 7.30–7.56 (8H, m, H-
Ph), 8.11–8.13 (2H, m, H-Ph); 13C NMR: ꢀ 19.5 (t, C-5),
24.7 (q, C-12), 26.5 (q, C-14), 28.1 (q, C-15), 32.0 (s, C-11),
35.2 (s, C-6), 37.6 (d, C-9), 37.6 (s, C-7), 39.6 (t, C-1), 42.1
(t, C-10), 44.3 (d, C-2), 68.0 (t, C-13), 69.3 (s, C-3), 71.2 (d,
C-8), 74.7 (d, C-30), 82.9 (d, C-20), 125.9 (s, C-Ph), 126.4
(d, C-Ph), 128.2 (d, C-Ph), 128.5 (d, C-Ph), 128.9 (d, C-
Ph), 129.0 (d, C-Ph), 132.2 (d, C-Ph), 140.6 (s, C-Ph),
163.4 (s, NCO), 170.1 (s, C-10), 173.6 (s, C-4); LSIMS
m/z (rel. int.): 516 [M+H]+ (100), 498 (26), 474 (2), 403
(2), 307 (12), 289 (7), 268 (100), 225 (52), 193 (8), 154
(92); HR LSIMS m/z: [M+H]+ calc. for C31H34O6N:
516.23861, found: 516.23963.
4.4.6. Compound 23
4.4.4. Compound 17
TLC Rf=0.62 (hexane–EtOAc 8:2); mp 127–131 C;
TLC Rf=0.27, (hexane–EtOAc 7:3); mp 64–68 ꢀC;
[a]2D0=À21.2ꢀ (CHCl3, c 1.0); UV lmax (EtOH) nm: 242 ("
16768); IR ꢁmax (CHCl3) cmÀ1: 3066, 2955, 2867, 1960,
1748, 1654; 1H NMR: ꢀ 0.95 (3H, s, H-15), 1.00 (3H, s, H-
14), 1.05 (3H, s, H-12), 1.41 (1H, dd, J10a,10b=12.6 Hz and
ꢀ
[a]2D0=À57.83ꢀ (CHCl3, c 1.0); UV lmax (EtOH) nm: 241
(" 15984); IR ꢁmax (CHCl3) cmÀ1: 3066, 2955, 2867, 1960,
1748, 1654; 1H NMR: ꢀ 0.90 (3H, s, H-15), 1.12 (3H, s, H-
14), 1.46 (1H, dd, J10b,10a=12.6 Hz, J10b,9a=8.3 Hz, H-
10b), 1.75 (3H, s, H-12), 1.91 (1H, ddd, J10a,10b=12.6 Hz,
J
10a,9b=10.6 Hz, H-10a), 1.50 (1H, dd, J1b,1a=12.9 Hz
and J1b,2a=10.8 Hz, H-1b), 1.70 (1H, dd, J10b,10a=12.6
Hz and 10b,9b=7.0 Hz, H-10b), 1.80 (1H, dd,
1a,1b=12.9 Hz and J1a,2a=8.1 Hz, H-1a), 2.02–2.10
(1H, m, H-9b), 2.13–2.19 (1H, m, H-2a), 2.59 (1H, d,
J
J
10a,9a=7.9 Hz and J=2.0 Hz, H-10a), 2.07 (1H, d,
1b,1a=15.0 Hz, H-1b), 2.20 (1H, d, J1a,1b=15.0 Hz, H-
J
J
1a), 2.91 (1H, d, J4b,4a=16.1 Hz, H-4b), 3.25–3.31 (1H,
m, H-9a), 3.40 (1H, d, J4a,4b=16.1 Hz, H-4a), 4.94 (1H,
J
4b,4a=14.1 Hz, H-4b), 2.69 (1H, d, J4a,4b=14.1 Hz, H-
0
0
0
0
0
0
0
0
0
d, J2 ,3 =6.3 Hz, H-2 ), 5.47 (1H, d, J3 ,2 =6.3 Hz, H-3 ),
5.82 (1H, d, J8b,9a=11.4 Hz, H-8b), 7.13 (1H, t, J=1.5
Hz, H-5a), 7.28–7.55 (9H, m, H-13 and H-Ph), 8.07–
8.12 (2H, m, H-Ph); 13C NMR: ꢀ 21.5 (q, C-12), 27.5 (q,
C-14), 28.7 (q, C-15), 29.4 (t, C-4), 37.6 (s, C-11), 44.6
(d, C-9), 45.8 (t, C-10), 46.5 (t, C-1), 73.6 (d, C-8), 74.7
(d, C-30), 83,2 (d, C-20), 121.3 (s, C-6), 124.2 (s, C-7),
126.4 (d, C-Ph), 128.0 (d, C-Ph), 128.4 (d, C-Ph), 128.7
(d, C-Ph), 128.8 (d, C-Ph), 130.0 (s, C-3), 131.9 (d, C-
4a), 4.98 (1H, d, J2 ,3 =6.4 Hz, H-2 ), 5.49 (1H, d,
0
0
0
J3 ,2 =6.4 Hz, H-3 ), 5.86 (1H, d, J8a,9b=10.3 Hz, H-
8a), 7.16 (1H, s, H-5), 7.20 (1H, s, H-13), 7.30–7.57 (8H,
m, H-Ph), 8.09–8.14 (2H, m, H-Ph); 13C NMR: ꢀ 20.7
(q, C-12), 31.0 (q, C-15), 31.2 (q, C-14), 34.7 (s, C-11),
40.1 (t, C-4), 43.2 (t, C-1), 46.1 (t, C-10), 46.5 (d, C-9),
55.1 (d, C-2), 73.3 (s, C-3), 74.8 (d, C-30), 75.7 (d, C-8),
83.3 (d, C-20), 119.1 (s, C-6), 124.9 (s, C-7), 126.5 (d, C-
Ph), 126.7 (s, C-Ph), 128.2 (d, C-Ph), 128.5 (d, C-Ph),