K. Takeda, M. Toyota / Tetrahedron 67 (2011) 9909e9921
9919
1252,1231, 1108 cmꢀ1; HRMS (EI) m/z 279 (M)þ calcd for C16H25NO3
279.1834, found 279.1837.
4.0 Hz), 2.72 (1H, dddd, J 8.8, 6.8, 5.2, 5.2 Hz), 2.56e2.39 (2H, m),
1.87 (1H, dddd, J 14.0, 6.0, 6.0, 4.0 Hz), 1.82 (1H, dddd, J 13.2, 9.2, 6.8,
6.8 Hz), 1.61e1.44 (2H, m), 1.41 (9H, s); 13C NMR (100 MHz, CDCl3)
4.2.52. Isopropyl (1R*,5S*)-3-tert-butyl-8-methyl-2-oxo-3-aza-bicy-
d 173.0, 168.1, 148.7, 111.9, 66.3, 57.7, 52.8, 43.1, 42.2, 31.1, 28.9, 28.3,
clo[3.3.0]octa-7-ene-1-carboxylate (34e). 1H NMR (400 MHz, CDCl3)
27.6; IR (neat) 1740, 1639, 1240, 1199 cmꢀ1; HRMS (EI) m/z 265 (M)þ
d
5.52e5.49 (1H, m), 5.04 (1H, qq, J 6.4, 6.4 Hz), 3.73e3.67 (1H, m),
calcd for C15H23NO3 265.1678, found 265.1671.
3.06e2.99 (2H, m), 2.65 (1H, dddq, J 16.4, 8.0, 2.4, 2.4 Hz), 2.09 (1H,
dddq, J 16.4, 2.4, 2.4, 2.4 Hz), 1.94 (3H, ddd, J 2.4, 2.4, 1.6 Hz), 1.38
(9H, s), 1.25 (3H, d, J 6.4 Hz), 1.24 (3H, d, J 6.4 Hz); 13C NMR
4.2.58. Methyl (1R*,6R*)-3-tert-butyl-9-methyl-2-oxo-3-azabicyclo
[4.3.0]nona-8-ene-1-carboxylate (37c). 1H NMR (400 MHz, CDCl3)
(100 MHz, CDCl3)
d 171.1, 170.7, 137.9, 127.9, 71.2, 67.7, 54.4, 50.9,
d
5.63e5.60 (1H, m), 3.73 (3H, s), 3.34e3.29 (2H, m), 2.88 (1H, dddd,
40.7, 38.1, 27.6, 21.9, 21.8,14.1; IR (neat) 2978, 1737,1684,1281,1260,
1235, 1109 cmꢀ1; HRMS (EI) m/z 279 (M)þ calcd for C16H25NO3
279.1834, found 279.1834.
J 8.8, 5.6, 5.6, 4.0 Hz), 2.58 (1H, dddq, J 16.8, 8.8, 2.4, 2.4 Hz),
2.05e1.94 (2H, m), 1.86 (3H, ddd, J 2.4, 2.4, 1.6 Hz), 1.65 (1H, dddd, J
13.6, 5.6, 5.6, 3.6 Hz),1.41 (9H, s); 13C NMR (100 MHz, CDCl3)
d 173.8,
168.6, 139.1, 129.6, 70.7, 57.8, 52.4, 41.6, 41.0, 37.1, 30.6, 28.4, 15.2; IR
(neat) 1750, 1641, 1245, 1200 cmꢀ1; HRMS (EI) m/z 265 (M)þ calcd
for C15H23NO3 265.1678, found 265.1671.
4.2.53. Methyl (1R*,6R*)-3-methyl-9-methylene-2-oxo-3-azabicyclo
[4.3.0]nonane-1-carboxylate (36a). 1H NMR (400 MHz, CDCl3)
d
5.52 (1H, dd, J 2.0, 2.0 Hz), 5.22 (1H, dd, J 2.0, 2.0 Hz), 3.73 (3H, s),
3.40 (1H, ddd, J 12.0, 9.6, 2.4 Hz), 3.29 (1H, ddd, J 12.0, 5.2, 5.2 Hz),
2.98 (3H, s), 2.72 (1H, dddd, J 10.4, 6.4, 4.0, 4.0 Hz), 2.62e2.52 (1H,
m), 2.51e2.41 (1H, m), 1.89e1.75 (2H, m), 1.66 (1H, dddd, J 13.6,
10.0, 10.0, 4.8 Hz), 1.57 (1H, dddd, J 12.8, 8.8, 5.2, 4.0 Hz); 13C NMR
4.2.59. Benzyl (1R*,6R*)-3-methyl-9-methylene-2-oxo-3-azabicyclo
[4.3.0]nonane-1-carboxylate (36d). 1H NMR (400 MHz, CDCl3)
d
7.38e7.28 (5H, m), 5.56 (1H, dd, J 2.4, 2.4 Hz), 5.23 (1H, dd, J 2.0,
2.0 Hz), 5.22 (1H, d, J 12.4 Hz), 5.13 (1H, d, J 12.4 Hz), 3.37 (1H, ddd, J
12.0, 9.6, 4.4 Hz), 3.27 (1H, ddd, J 12.0, 4.8, 4.8 Hz), 2.98 (3H, s), 2.70
(1H, dddd, J 10.4, 6.0, 4.4, 4.4 Hz), 2.53 (1H, ddddd, J 16.4, 9.6, 5.2,
2.4, 2.4 Hz), 2.46(1H, ddddd, J 16.4, 8.0, 8.0, 2.0, 2.0 Hz), 1.81 (1H,
dddd, J 14.0, 4.8, 4.8, 4.8 Hz), 1.77e1.59 (2H, m), 1.53 (1H, dddd, J
(100 MHz, CDCl3)
d 172.6, 167.1, 147.8, 112.6, 64.4, 53.0, 48.3, 44.1,
35.5, 30.1, 28.3, 25.3; IR (neat) 2950, 1739, 1643, 1253, 1194 cmꢀ1
;
HRMS (EI) m/z 223 (M)þ calcd for C12H17NO3 223.1208, found
223.1205.
12.8, 8.4, 5.2, 4.0 Hz); 13C NMR (100 MHz, CDCl3)
d 171.9, 167.0,
4.2.54. Methyl (1R*,6R*)-3,9-dimethyl-2-oxo-3-azabicyclo[4.3.0]nona-
147.6, 136.2, 128.6, 128.1, 127.9, 112.7, 67.1, 64.5, 48.3, 44.1, 35.5, 30.2,
28.3, 25.3; IR (neat) 1739, 1641, 1221, 1189 cmꢀ1; HRMS (EI) m/z 299
(M)þ calcd for C18H21NO3 299.1521, found 299.1523.
8-ene-1-carboxylate (37a). 1H NMR (400 MHz, CDCl3)
d 5.63e5.60
(1H, m), 3.73(3H, s), 3.41 (1H, ddd, J 12.8, 8.8, 3.6 Hz), 3.29 (1H,
ddd, J 12.8, 6.4, 4.0 Hz), 2.97 (3H, s) 2.86 (1H, dddd, J 8.4, 6.0, 5.2,
5.2 Hz), 2.55e2.46 (1H, m), 2.16e2.02 (2H, m), 1.90 (3H, ddd, J
2.0, 2.0, 2.0 Hz), 1.72 (1H, dddd, J 13.6, 6.4, 6.4, 4.0); 13C NMR
4.2.60. Benzyl (1R*,6R*)-3,9-dimethyl-2-oxo-3-azabicyclo[4.3.0]nona-
8-ene-1-carboxylate (37d). 1H NMR (400 MHz, CDCl3)
d 7.38e7.27
(100 MHz, CDCl3)
d 173.4, 167.2, 139.5, 129.2, 67.4, 52.7, 46.9, 42.9,
35.9, 35.5, 26.7, 15.4; IR (neat) 2950, 1739, 1642, 1249, 1210 cmꢀ1
;
(5H, m), 5.62e5.59 (1H, m), 5.27 (1H, d, J 12.4 Hz), 5.11 (1H, d, J
12.4 Hz), 3.39 (1H, ddd, J 12.4, 8.8, 3.6 Hz), 3.27 (1H, ddd, J 12.4, 6.4,
4.4 Hz), 2.98 (3H, s), 2.83 (1H, dddd, J 8.4, 6.4, 5.2, 5.2 Hz), 2.48 (1H,
dddq, J 16.4, 8.4, 2.4, 2.4 Hz), 2.10 (1H, dddq, J 16.4, 2.4, 2.4, 2.4 Hz),
2.04 (1H, ddd, J 13.2, 9.2, 4.4 Hz),1.92 (3H, ddd, J 2.4, 2.4,1.6 Hz),1.70
(1H, dddd, J 13.2, 6.4, 6.4, 4.0 Hz); 13C NMR (100 MHz, CDCl3)
HRMS (EI) m/z 223 (M)þ calcd for C12H17NO3 223.1208, found
223.1202.
4.2.55. Methyl (1R*,6R*)-3-benzyl-9-methylene-2-oxo-3-azabicyclo
[4.3.0]nonane-1-carboxylate (36b). 1H NMR (400 MHz, CDCl3)
d
172.7, 167.1, 139.4, 136.2, 129.2, 128.6, 128.1, 127.9, 67.4, 66.9, 47.0,
d
7.34e7.22 (5H, m), 5.60 (1H, dd, J 2.4, 2.4 Hz), 5.27 (1H, dd, J 2.0,
42.9, 35.9, 35.5, 26.8, 15.4; IR (neat) 1737, 1640, 1238, 1208 cmꢀ1
;
2.0 Hz), 4.71 (1H, d, J 14.8 Hz), 4.54 (1H, d, J 14.8 Hz), 3.76 (3H, s),
3.28 (1H, ddd, J 12.4, 10.0, 4.0 Hz), 3.20 (1H, ddd, J 12.4, 4.8, 4.8 Hz),
2.74 (1H, dddd, J 10.4, 6.0, 4.0, 4.0 Hz), 2.58(1H, ddddd, J 16.8, 9.6,
5.6, 2.4, 2.4 Hz), 2.49 (1H, ddddd, J 16.8, 8.0, 8.0, 2.0, 2.0 Hz),
1.87e1.76 (2H, m), 1.64e1.51 (2H, m); 13C NMR (100 MHz, CDCl3)
HRMS (EI) m/z 299 (M)þ calcd for C18H21NO3 299.1521, found
299.1523.
4.2.61. Isopropyl (1R*,6R*)-3-methyl-9-methylene-2-oxo-3-
azabicyclo[4.3.0]nonane-1-carboxylate (36e). 1H NMR (400 MHz,
d
172.6, 167.2, 147.9, 137.2, 128.7, 128.0, 127.5, 112.7, 64.6, 53.0, 50.5,
45.5, 44.0, 30.2, 28.4, 25.5; IR (neat) 1740, 1638, 1254 cmꢀ1; HRMS
CDCl3)
d 5.50 (1H, dd, J 2.0, 2.0 Hz), 5.19 (1H, dd, J 2.0, 2.0 Hz), 5.02
(EI) m/z 299 (M)þ calcd for C18H21NO3 299.1521, found 299.1523.
(1H, sept, J 6.0 Hz), 3.39 (1H, ddd, J 12.4, 10.0, 4.4 Hz), 3.28 (1H, ddd,
J 12.4, 4.8, 4.8 Hz), 2.97 (3H, s), 2.71 (1H, dddd, J 10.4, 6.4, 4.4,
4.4 Hz), 2.54 (1H, ddddd, J 16.8, 9.6, 5.6, 2.0, 2.0 Hz), 2.45 (1H,
ddddd, J 16.8, 8.4, 8.4, 2.0, 2.0 Hz),1.88e1.74 (2H, m),1.65 (1H, dddd,
J 14.0, 10.0, 10.0, 4.8 Hz), 1.54 (1H, dddd, J 12.8, 8.4, 5.2, 4.0 Hz), 1.23
(3H, d, J 6.0 Hz), 1.20 (3H, d, J 6.0 Hz); 13C NMR (100 MHz, CDCl3)
4.2.56. Methyl (1R*,6R*)-3-tert-butyl-9-methyl-2-oxo-3-azabicyclo
[4.3.0]nona-8-ene-1-carboxylate (37b). 1H NMR (400 MHz, CDCl3)
d
7.35e7.22 (5H, m), 5.67e5.64 (1H, m), 4.68 (1H, d, J 15.2 Hz), 4.56
(1H, d, J 15.2 Hz), 3.77 (3H, s), 3.28 (1H, ddd, J 12.4, 8.8, 4.0 Hz), 3.21
(1H, ddd, J 12.4, 6.4, 4.4 Hz), 2.88 (1H, dddd, J 8.4, 6.0, 5.2, 5.2 Hz),
2.53 (1H, dddq, J 16.4, 8.4, 2.0, 2.0 Hz), 2.10 (1H, dddq, J 16.4, 2.4, 2.4,
2.4 Hz), 2.01 (1H, ddd, J 13.6, 9.2, 4.4 Hz), 1.95 (3H, ddd, J 2.0, 2.0,
2.0 Hz), 1.67 (1H, dddd, J 13.6, 6.4, 6.4, 4.4 Hz); 13C NMR (100 MHz,
d
171.5,167.2,147.8,112.3, 69.0, 64.6, 48.2, 44.1, 35.4, 30.3, 28.4, 25.4,
21.8, 21.6; IR (neat) 1733, 1644, 1254, 1108 cmꢀ1; HRMS (EI) m/z 251
(M)þ calcd for C14H21NO3 251.1521, found 251.1510.
4.2.62. Isopropyl (1R*,6R*)-3,9-dimethyl-2-oxo-3-azabicyclo[4.3.0]
CDCl3) d 173.4,167.3,139.3,137.2,129.5,128.7,127.9,127.5, 67.7, 52.7,
nona-8-ene-1-carboxylate (37e). 1H NMR (400 MHz, CDCl3)
50.6, 44.3, 42.9, 36.1, 27.1, 15.4; IR (neat) 1740, 1637, 1247 cmꢀ1
;
HRMS (EI) m/z 299 (M)þ calcd for C18H21NO3 299.1521, found
d
5.59e5.56 (1H, m), 5.03 (1H, sept, J 6.4 Hz), 3.39 (1H, ddd, J 12.8,
9.2, 4.0 Hz), 3.27 (1H, ddd, J 12.8, 6.4, 4.4 Hz), 2.96 (3H, s), 2.83 (1H,
dddd, J 8.4, 6.0, 5.2, 5.2 Hz), 2.48 (1H, dddq, J 16.4, 8.8, 2.0, 2.0 Hz),
2.15e2.02 (2H, m), 1.91 (3H, ddd, J 2.4, 2.4, 1.6 Hz), 1.71 (1H, dddd, J
12.4, 6.4, 6.4, 4.0 Hz), 1.24 (3H, d, J 6.4 Hz), 1.20 (3H, d, J 6.4 Hz); 13C
299.1517.
4.2.57. Methyl (1R*,6R*)-3-tert-butyl-9-methylene-2-oxo-3-
azabicyclo[4.3.0]nonane-1-carboxylate (36c). 1H NMR (400 MHz,
NMR (100 MHz, CDCl3)
d 172.4, 167.4, 139.7, 128.8, 68.7, 67.4, 46.9,
CDCl3)
d 5.43 (1H, dd, J 2.0, 2.0 Hz), 5.20 (1H, dd, J 2.0, 2.0 Hz), 3.72
43.0, 35.8, 35.4, 26.6, 21.8, 21.7, 15.5; IR (neat) 1733, 1644, 1248,
(3H, s), 3.38 (1H, ddd, J 12.4, 6.0, 4.4 Hz), 3.26 (1H, ddd, J 12.4, 9.2,