9160
F.I. Zubkov et al. / Tetrahedron 67 (2011) 9148e9163
OMe), 3.41 (1H, br s, H-7a), 2.97 (1H, d, J7a,10a 4.1 Hz, H-10a), 2.14
(1H, m, H-6), 2.12 (3H, s, OAc), 2.05 (3H, s, OAc), 2.04 (3H, s, OAc),
2.02 (3H, s, OAc), 1.71 (1H, m, H-10A), 1.55 (3H, s, Me), 1.34 (1H, m,
30), 3.69 (3H, s, OMe), 3.38 (1H, dd, J7a,10a 4.5, J10,10a 11.5 Hz, H-10a),
3.31 (1H, br d, J7a,10a 4.5 Hz, H-7a), 3.29 (1H, d, J10,10a 11.5 Hz, H-10),
2.12 (3H, s, OAc), 2.06 (3H, s, OAc), 2.05 (3H, s, OAc), 2.01 (3H, s,
OAc), 1.82 (1H, m, H-6), 1.60 (2H, m, H-20), 1.41 (1H, m, H-10A), 1.13
H-10B); 13C NMR (CDCl3, 100.6 MHz)
d 171.3, 170.6, 170.3, 170.1
(OCOMeꢃ4), 167.7 (CO2Me), 166.6 (C11), 138.3 (C12a), 131.0 (C4),
(1H, m, H-10B); 13C NMR (CDCl3, 100.6 MHz)
d 171.1, 170.8, 170.1,
128.7 (C2), 125.3 (C3), 125.0 (C1), 123.3 (C4a), 103.2 (C7), 83.9 (C9),
167.9 (OCOMeꢃ4), 167.5 (CO2Me), 166.3 (C11), 138.3 (C12a), 131.1
0
75.4 (C8), 70.6 (C5), 61.5 (C2 ), 58.6 (C6a), 54.0 (C10), 52.7 (CO2Me),
(C4), 128.9 (C2), 125.5 (C3), 125.1 (C1), 123.7 (C4a), 104.2 (C7), 80.2
0
0
48.7 (C7a), 46.0 (C10a), 37.3 (C6), 26.0 (Me), 24.3 (C1 ), 21.7, 21.1, 20.8,
(C9), 76.9 (C8), 70.7 (C5), 63.4 (C3 ), 58.8 (C6a), 52.7 (CO2Me), 46.8
0
20.7 (OCOMeꢃ4). Anal. Calcd for C29H33NO12: C, 59.28; H, 5.66; N,
(C10), 46.3 (C7a), 39.7 (C10a), 39.5 (C6), 25.5 (C1 ), 21.9, 21.3, 20.9, 20.8
0
2.38. Found: C, 59.42; H, 5.49; N, 2.47.
(OCOMeꢃ4), 21.0 (C2 ). Anal. Calcd for C29H33NO12: C, 59.28; H,
5.66; N, 2.38. Found: C, 59.42; H, 5.31; N, 2.50.
3.10.5. (5S*,6R*,6aR*,7R*,7aR*,8R*,9S*,10aR*)-6-(2-Acetoxyethyl)-
10a-methyl-11-oxo-6,6a,7a,8,9,10,10a,11-octahydro-7,9-
epoxycyclopenta[4,5]pyrido[1,2-a]quinoline-5,7,8(5H)-triyl triacetate
(18d). Colourless druses; yield 0.32 g (41%); mp 193e194 ꢀC
(decomp.); IR (KBr): 1679 (NC]O), 1747 (OC]O) cmꢁ1; HRMS
(DART) m/z (rel intensity): 530.204(7) [MþH]þ (100) (exact mass for
C27H32NO10 530.2026), 531.21 (30), 532.21 (6), 533.21 (1); 1H NMR
3.10.8. (5R*,6aR*,7S*,7aS*,8S*,9R*,10aR*)-11-Oxo-5-(2-
oxopyrrolidin-1-yl)-6,6a,7a,8,9,10,10a,11-octahydro-7,9-
epoxycyclopenta[4,5]pyrido[1,2-a]quinoline-7,8(5H)-diyl
diacetate
(21a). Colourless druses; yield 0.32 g (47%); mp 234e236 ꢀC
(decomp.); IR 1687, 1662 (NC]O), 1735 (OC]O) cmꢁ1; EIMS
(70 eV) m/z (rel intensity): Mþ 454 (1), 394 (88), 351 (17), 338 (26),
305 (35), 281 (26), 267 (25), 250 (55), 238 (27), 222 (91), 196 (21),
(CDCl3, 400 MHz) d 8.03 (1H, d, J1,2 8.1 Hz, H-1), 7.28 (1H, d, J3,4 7.5 Hz,
H-4), 7.27 (1H, dd, J2,3 7.5, J1,2 8.1 Hz, H-2), 7.06 (1H, t, J2,3¼J3,4¼7.5 Hz,
H-3), 5.78 (1H, d, J5,6 1.9 Hz, H-5), 5.09 (1H, s, H-6a), 4.62 (1H, br s, H-
9), 4.57 (1H, br s, H-8), 4.13 (2H, m, H-20), 3.72 (1H, br s, H-7a), 2.41
(1H, m, H-6), 2.23 (1H, m, H-10A), 2.21 (1H, d, J10A,10B 13.7 Hz, H-10A),
2.06 (3H, s, OAc), 2.02 (3H, s, OAc),1.98 (3H, s, OAc),1.95 (3H, s, OAc),
1.72 (1H, d, J10A,10B 13.7 Hz, H-10B),1.13 (1H, m, H-10B); 13C NMR
156 (17), 130 (100), 43 (55); 1H NMR (CDCl3, 400 MHz)
d 7.95 (1H,
dd, J1,3 1.2, J1,2 8.5 Hz, H-1), 7.18 (1H, ddd, J2,4 1.8, J2,3 7.2, J1,2 8.5 Hz,
H-2), 7.06 (1H, ddd, J1,3 1.2, J2,3 7.2, J3,4 7.8 Hz, H-3), 6.98 (1H, br d, J3,4
7.8 Hz, H-4), 5.55 (1H, dd, J5,6A 7.5, J5,6B 11.8 Hz, H-5), 4.88 (1H, d,
J7a,8 1.9 Hz, H-8), 4.59 (1H, br s, H-9), 4.27 (1H, dd, J6a,6A 1.5, J6a,6B
11.8 Hz, H-6a), 3.93 (1H, dd, J7a,8 1.9, J7a,10a 4.9 Hz, H-7a), 3.18 (1H, m,
H-50A), 3.18 (1H, m, H-10a), 2.98 (1H, m, H-50B), 2.43 (2H, m, H-30),
2.40 (1H, ddd, J6a,6A 1.5, J5,6A 7.5, J6A,6B 13.4 Hz, H-6A), 2.24 (1H, ddd,
J9,10A 1.4, J10A,10a 12.0, J10A,10B 13.7 Hz, H-10A), 2.06 (3H, s, OAc), 2.06
(3H, s, OAc), 2.02 (1H, dt, J6a,6B¼J5,6B¼11.8, J6A,6B 13.4 Hz, H-6B), 1.95
(2H, m, H-40), 1.66 (1H, ddd, J9,10B 1.5, J10B,10a 4.1, J10A,10B 13.7 Hz, H-
0
(CDCl3,100.6 MHz)
137.8 (C12a), 132.1 (C4), 129.2 (C2), 125.0 (C3), 123.5 (C4a), 123.3 (C1),
d
173.2,171.1,170.1,169.6 (OCOMeꢃ4),169.1 (C11),
0
106.9 (C7), 80.6 (C9), 76.8 (C8), 71.3 (C5), 62.8 (C2 ), 55.4 (C6a), 47.7
0
(C7a), 42.6 (C10a), 42.2 (C10), 35.3 (C6), 26.1 (Me), 24.8 (C1 ), 21.8, 21.3,
21.0, 21.0 (OCOMeꢃ4). Anal. Calcd for C27H31NO10: C, 61.24; H, 5.90;
N, 2.65. Found: C, 61.46; H, 6.02; N, 2.75.
10B); 13C NMR (CDCl3, 100.6 MHz)
d 175.6 (C2 ), 169.3 and 169.8
(OCOMeꢃ2), 168.0 (C11), 137.7 (C12a), 127.4 (C2), 127.3 (C4), 125.9
3.10.6. (5S*,6R*,6aR*,7R*,7aR*,8R*,9S*,10S*,10aS*)-6-(2-
Acetoxyethyl)-11-oxo-10-phenyl-6,6a,7a,8,9,10,10a,11-octahydro-7,9-
epoxycyclopenta[4,5]pyrido[1,2-a]quinoline-5,7,8(5H)-triyl triacetate
(18e). Colourless plates; yield 0.66 g (74%); mp 221e222 ꢀC; IR
1671 (NC]O), 1745 (OC]O) cmꢁ1; HRMS (DART) m/z (rel in-
tensity): 592.220(7) [MþH]þ (100) (exact mass for C32H34NO10
592.2183), 593.22 (35), 594.22 (8), 595.23 (1); 1H NMR (CDCl3,
00 00
(C4a), 125.5 (C3), 124.6 (C1), 105.7 (C7), 79.4 (C9), 77.3 (C8), 58.3 (C6a),
0
0
47.9 (C5), 42.1 (C5 ), 40.2 (C7a), 36.4 (C10a), 33.6 (C10), 31.0 (C3 ), 27.4
0
(C6), 20.7 and 21.8 (OCOMeꢃ2), 17.8 (C4 ). Anal. Calcd for
C24H26N2O7: C, 63.43; H, 5.77; N, 6.16. Found: C, 63.29; H, 5.85; N,
6.31.
3.10.9. (5R*,6aR*,7S*,7aS*,8S*,9R*,10aR*)-9-Methyl-11-oxo-5-(2-
oxopyrrolidin-1-yl)-6,6a,7a,8,9,10,10a,11-octahydro-7,9-
400 MHz) d 8.42 (1H, d, J1,2 8.2 Hz, H-1), 7.55 (2H, d, J2 ,3 7.6 Hz, H-
200(H-600)), 7.36 (m, 4H, H-4, H-400, H-300and H-500), 7.25 (1H, dd, J2,3
7.6, J1,2 8.2 Hz, H-2), 7.16 (1H, t, J2,3¼J3,4¼7.6 Hz, H-3), 5.88 (1H, d, J5,6
2.1 Hz, H-5), 5.13 (1H, s, H-6a), 5.09 (1H, d, J9,10 2.1 Hz, H-9), 4.67
(1H, br s, H-8), 4.23 (2H, m, H-20), 4.16 (1H, dd, J9,10 2.1, J10,10a 4.8 Hz,
H-10), 3.38 (1H, br d, J7a,10a 4.8 Hz, H-7a), 3.33 (1H, t,
J7a,10a¼J10,10a¼4.8 Hz, H-10a), 2.52 (1H, m, H-6), 2.38 (1H, m, H-10A),
2.14 (3H, s, OAc), 2.11 (3H, s, OAc), 2.04 (3H, s, OAc), 2.02 (3H, s, OAc),
epoxycyclopenta[4,5]pyrido[1,2-a]quinoline-7,8(5H)-diyl
diacetate
(21b). Colourless druses; yield 0.42 g (60%); mp 259e260 ꢀC
(decomp.); IR (KBr): 1679, 1654 (NC]O), 1741 (OC]O) cmꢁ1; EIMS
(70 eV) m/z (rel intensity): Mþ 468 (3), 408 (37), 349 (100), 295 (14),
282 (23), 264 (84), 236 (94), 211 (22), 196 (11), 180 (11), 130 (63), 78
(22), 69 (30), 55 (74), 43 (93); 1H NMR (CDCl3, 400 MHz)
d 8.00 (1H,
dd, J1,3 1.0, J1,2 8.4 Hz, H-1), 7.23 (1H, ddd, J2,4 1.0, J2,3 7.5, J1,2 8.4 Hz,
H-2), 7.10 (1H, dt, J1,3 1.0, J2,3¼J3,4¼7.5 Hz, H-3), 7.03 (1H, dd, J2,4 1.0,
J3,4 7.5 Hz, H-4), 5.59 (1H, dd, J5,6A 7.6, J5,6B 11.9 Hz, H-5), 4.94 (1H, d,
J7a,8 1.8 Hz, H-8), 4.29 (1H, dd, J6a,6A 1.4, J6a,6B 11.8 Hz, H-6a), 3.94
(1H, dd, J7a,8 1.8, J7a,10a 4.5 Hz, H-7a), 3.25 (1H, m, H-50A), 3.21 (1H,
dt, J7a,10a¼J10B,10a¼4.5, J10A,10a 12.2 Hz, H-10a), 3.04 (1H, m, H-50B),
2.49 (2H, m, H-30), 2.43 (1H, ddd, J6a,6A 1.4, J5,6A 7.6, J6A,6B 13.4 Hz, H-
6A), 2.24 (1H, dd, J10A,10a 12.2, J10A,10B 13.3 Hz, H-10A), 2.13 (3H, s,
OAc), 2.10 (3H, s, OAc), 2.04 (1H, dt, J6a,6B¼J5,6B¼11.8, J6A,6B 13.4 Hz,
H-6B), 2.01 (2H, m, H-40), 1.69 (1H, dd, J10B,10a 4.5, J10A,10B 13.3 Hz, H-
0
1.26 (1H, m, H-10B); 13C NMR (CDCl3, 100.6 MHz)
d
170.9, 170.1,
00
169.4, 169.3 (OCOMeꢃ4), 169.0 (C11), 139.5 (C12a), 137.7 (C1 ), 132.2
00
00
00
00
00
(C4), 129.3 (C4 ), 129.0 (C3 (C5 )), 127.2 (C2), 126.9 (C2 (C6 )), 125.2
(C3), 123.4 (C4a), 122.9 (C1), 106.8 (C7), 82.2 (C9), 76.2 (C8), 71.3 (C5),
0
62.7 (C2 ), 56.2 (C6a), 50.7 (C10), 46.4 (C7a), 41.7 (C10a), 35.2 (C6), 24.9
0
(C1 ), 21.6, 21.2, 20.9, 20.8 (OCOMeꢃ4). Anal. Calcd for C32H33NO10
:
C, 64.97; H, 5.62; N, 2.37. Found: C, 64.75; H, 5.43; N, 2.36.
3.10.7. Methyl (5S*,6R*,6aR*,7R*,7aR*,8R*,9S*,10S*,10aR*)-5,7,8-
triacetoxy-6-(3-acetoxypropyl)-11-oxo-5,6,6a,7,7a,8,9,10,10a,11-
decahydro-7,9-epoxycyclopenta[4,5]pyrido[1,2-a]quinoline-10-
10B), 1.55 (3H, m, Me); 13C NMR (CDCl3, 100.6 MHz)
d 175.9 (C2 ),
169.6 and 169.8 (OCOMeꢃ2), 168.5 (C11), 137.9 (C12a), 127.7 (C2),
carboxylate (18f). Colourless plates; yield 0.32
g
(36%); mp
127.5 (C4),126.2 (C4a),125.7 (C3),124.9 (C1),106.1 (C7), 87.0 (C9), 77.9
282e283 ꢀC (decomp.); IR 1667 (NC]O), 1732 and 1749 (OC]O)
cmꢁ1; EIMS (70 eV) m/z (rel intensity): Mþ 587 (3), 527 (7), 485
(31), 426 (100), 384 (27), 342 (11), 255 (13), 230 (66), 170 (7), 130
(C8), 58.6 (C6a), 48.2 (C5), 42.4 (C5 ), 41.8 (C7a), 39.1 (C10), 36.7 (C10a),
0
0
0
31.2 (C3 ), 27.6 (C6), 22.2 and 20.9 (OCOMeꢃ2), 18.0 (C4 ), 15.1 (Me).
Anal. Calcd for C25H28N2O7: C, 64.09; H, 6.02; N, 5.98. Found: C,
63.89; H, 5.97; N, 6.20.
(15), 113 (8), 43 (52); 1H NMR (CDCl3, 400 MHz)
d 7.94 (1H, d, J1,2
8.3 Hz, H-1), 7.35 (1H, dd, J2,3 7.6, J1,2 8.3 Hz, H-2), 7.23 (1H, d, J3,4
7.6 Hz, H-4), 7.16 (1H, t, J2,3¼J3,4¼7.6 Hz, H-3), 5.62 (1H, s, H-5), 5.09
(1H, s, H-6a), 4.91 (1H, br s, H-8), 4.87 (1H, s, H-9), 4.05 (2H, m, H-
3.10.10. (5R*,6aR*,7S*,7aS*,8S*,9R*,10aR*)-10a-Methyl-11-oxo-5-(2-
oxopyrrolidin-1-yl)-6,6a,7a,8,9,10,10a,11-octahydro-7,9-