T. Kobayashi et al. / Journal of Organometallic Chemistry 624 (2001) 73–87
85
4.6.12. 2-Phenyl-7-oxabicyclo[3.3.0]oct-1-en-3-one (2l)
[12a]
4.6.16. (5R*,8S*)-8-tert-Butyldimethylsiloxy-2,7,7-
trimethylbicyclo[3.3.0]oct-1-en-3-one (2p) [9]
Colorless oil; IR (neat) 1707, 1026 cm−1; H-NMR
l=2.32 (dd, J=3.5, 17.6 Hz, 1H), 2.83 (ddd, J=0.4,
6.3, 17.6 Hz, 1H), 3.22 (dd, J=7.8, 11.2 Hz, 1H),
3.26–3.35 (m, 1H), 4.35 (dd, J=7.7, 7.7 Hz, 1H), 4.57
(d, J=16.3 Hz, 1H), 4.92 (d, J=16.3 Hz, 1H), 7.31–
7.34 (m, 1H), 7.37–7.41 (m, 2H), 7.50 (dd, J=1.4, 7.9
Hz, 2H); 13C-NMR l=40.3, 43.3, 66.3, 71.3, 128.0,
128.6, 128.6, 130.5, 134.7, 177.4, 206.8.
Brown oil; IR (neat) 2954, 2929, 1712, 1678, 1090,
1
1
1068, 858, 837, 775 cm−1; H-NMR l=0.00 (s, 3H),
0.09 (s, 3H), 0.79 (s, 9H), 0.86 (s, 3H), 1.02 (dd, J=7.1,
12.9 Hz, 1H), 1.10 (s, 3H), 1.74 (d, J=2.3 Hz, 3H),
1.97 (dd, J=3.0, 18.0 Hz, 1H), 1.99 (dd, J=11.0, 12.9
Hz, 1H), 2.69 (dd, J=6.6, 18.0 Hz, 1H), 3.18–3.25
(brs, 1H), 4.05–4.08 (brs, 1H); 13C-NMR l= −4.9,
−4.6, 8.8, 18.2, 24.0, 25.7 (probably 2 carbons over-
lapped), 29.0, 39.3, 43.1, 44.0, 45.2, 76.2, 132.0, 180.7,
211.6.
4.6.13. 7-(4-Methylphenylsulfonyl)-2-phenyl-7-
azabicyclo[3.3.0]oct-1-en-3-one (2m) [10b,10j ]
Colorless crystals; mp 139–142°C (hexane–Et2O)
(lit., 120°C [10b], 165.2–166.5°C [10j]); IR (KBr) 1705,
4.6.17. (5R*,8R*)-8-tert-Butydimethylsiloxy-2,7,7-
trimethylbicyclo[3.3.0]oct-1-en-3-one (2q) [9]
Brown oil; IR (neat) 2956, 2931, 2860, 1713, 1672,
1
1348, 1168, 1157 cm−1; H-NMR l=2.23 (dd, J=3.7,
1
1134, 837, 775 cm−1; H-NMR l=0.11 (s, 6H), 0.82
17.8 Hz, 1H), 2.38 (s, 3H), 2.59 (dd, J=9.4, 10.9 Hz,
1H), 2.77 (dd, J=6.5, 17.8 Hz, 1H), 3.14–3.22 (m,
1H), 4.03–4.08 (m, 2H), 4.61 (d, J=16.9 Hz, 1H), 7.28
(d, J=8.2 Hz, 2H), 7.33–7.44 (m, SH), 7.69 (d, J=8.2
Hz, 2H); 13C-NMR l=21.5, 40.7, 41.8, 48.3, 52.0,
127.4, 128.2, 128.7, 128.9, 129.9, 130.0, 133.8, 136.1,
144.0, 171.8, 205.4.
(s, 3H), 0.94 (s, 9H), 1.14 (s, 3H), 1.23 (dd, J=8.3, 13.2
Hz, 1H), 1.81 (dd, J=1.8, 1.8 Hz, 3H), 1.93 (dd, 10.0,
13.2 Hz, 1H), 1.95 (dd, J=3.0, 17.9 Hz, 1H), 2.62 (dd,
J=6.7, 17.0, 1H), 2.74–2.83 (brs, 1H), 4.52–4.56 (brs,
1H); 13C-NMR l= −4.6, −4.5, 7.8, 18.0, 24.5, 25.9
(probably 2 carbons overlapped), 28.8, 35.2, 43.3, 43.7,
43.9, 80.4, 132.2, 179.9, 210.7.
4.6.14. Diethyl 8-oxo-9-phenylbicyclo[4.3.0]non-1(9)-
ene-3,3-dicarboxylate (2n)
4.6.18. Diethyl 8-(2,2-bis(ethoxycarbonyl)-4-pentenyl)-
7-oxobicyclo[5.3.0]deca-5,8-diene-3,3-dicarboxylate (4)
Colorless crystals; mp 104°C (hexane); IR (KBr)
Colorless oil; IR(neat) 1732, 1290, 1254, 1190 cm−1
;
1
1730, 1687, 1259, 1244, 1198 cm−1; H-NMR l=0.97
1H-NMR l=1.18–1.25 (m, 12H), 1.91 (dd, J=10.9,
12.9 Hz, 1H), 2.29–2.37 (m, 2H), 2.44 (dd, J=7.0, 14.3
Hz, 1H), 2.52 (dd, J=7.6, 14.3 Hz, 1H), 2.60 (d,
J=13.8 Hz, 1H), 2.61–2.65 (m, 1H), 2.90–2.99 (m,
1H), 3.16 (dt, Jd=18.8 Hz, Jt=2.3 Hz, 1H), 3.23 (d,
J=18.8 Hz, 1H), 3.30 (d, J=13.9 Hz, 1H), 4.03–4.23
(m, 8H), 5.04 (d, J=15.5 Hz, 1H), 5.04 (d, J=11.7 Hz,
1H), 5.66–5.75 (m, 1H), 6.06 (d, J=2.2 Hz, 1H), 6.51
(dd, J=4.4, 8.2 Hz, 1H); 13C-NMR l=13.9, 14.0
(probably 2 carbons overlapped), 32.2, 35.7, 37.6, 40.8,
41.4, 42.3, 58.0, 58.5, 61.0, 61.1, 61.9 (probably over-
lapped), 118.7, 126.0, 132.9, 139.4, 140.2, 162.8, 170.7,
170.8, 170.8, 170.9, 190.1; HRMS Found m/z 504.2361.
Calc. for C27H36O9: M, 504.2359.
(t, J=7.0 Hz, 3H), 1.20 (t, J=7.0 Hz, 3H), 1.38–1.47
(m, 1H), 1.92–1.98 (m, 1H), 2.11 (d, J=16.8 Hz, 1H),
2.17–2.22 (m, 1H), 2.50 (ddd, J=3.4, 5.5, 13.7 Hz,
1H), 2.66–2.77 (m, 3H), 3.67 (dd, J=2.1, 13.7 Hz,
1H), 3.91 (dq, Jd=10.7 Hz, Jq=7.0 Hz, 1H), 4.03 (dq,
Jd=10.7 Hz, Jq=7.0 Hz, 1H), 4.14 (dq, Jd=10.7 Hz,
Jq=7.0 Hz, 1H), 4.17 (dq, Jd=10.7 Hz, Jq=7.0 Hz,
1H), 7.28–7.32 (m, 3H), 7.37–7.40 (m, 2H); 13C-NMR
l=13.6, 13.9, 30.3, 30.7, 33.4, 39.0, 41.5, 56.2, 61.4,
61.9, 127.8, 128.3, 129.0, 130.9, 139.9, 170.0, 171.1,
171.4, 205.9; Anal. Found: C, 70.76; H, 6.88. Calc. for
C21H24O5: C, 70.77; H, 6.79%.
4.6.15. Diethyl 8-oxo-9-phenylbicyclo[4.3.0]non-1(9),
5-diene-3,3-dicarboxylate (2o)
4.6.19. Diethyl 4-methyl-3-(1-phenylethenyl)-3-
cyclopentene-1,1-dicarboxylate (5a)
This compound was so unstable that the yield was
determined by NMR with anthracene as an internal
standard. Colorless oil; IR (neat) 1734, 1695, 1252
After removal of 5b by HPLC, 5a was isolated in a
pure form. Colorless oil; IR(neat) 1732, 1254, 1184,
1
1
cm−1; H-NMR l=1.18 (t, J=7.1 Hz, 6H), 2.93 (d,
1070 cm−1; H-NMR l=1.23 (t, J=7.1 Hz, 6H), 1.52
J=4.4 Hz, 2H), 3.04 (s, 2H), 3.31 (s, 2H), 4.10–4.20
(m, 4H), 5.95 (t, J=4.3 Hz, 1H), 7.30–7.34 (m, 1H),
7.39–7.44 (m, 4H); 13C-NMR l=13.9, 31.0, 31.3, 38.5,
54.5, 61.9, 121.8, 128.1, 128.4, 128.9, 130.8, 134.9,
139.0, 160.3, 170.2, 202.9; HRMS Found m/z 354.1473.
Calc. for C21H22O5:M, 354.1467.
(s, 3H), 3.07 (brs, 2H), 3.10 (dd, J=1.8, 3.7Hz, 2H),
4.19 (q, J=7.1 Hz, 4H), 5.09 (d, J=1.5 Hz, 1H), 5.41
(d, J=1.6 Hz, 1H), 7.22–7.30 (m, 5H); 13C-NMR
l=14.0, 14.9, 44.5, 46.4, 57.4, 61.5, 114.8, 127.0, 127.5,
128.2, 132.6, 134.2, 140.4, 144.9, 172.2; HRMS Found
m/z 328.1688. Calc. for C20H24O4: M, 328.1675.