G. D. McAllister et al. / Tetrahedron 62 (2006) 6681–6694
6691
CDCl3) 1.49 (1H, app dt, J 4.5 and 8.2 Hz), 1.83 (1H, app dt, J
4.5 and 7.0 Hz), 2.30 (1H, dddd, J 7.0, 8.2, 10.4 and 11.0 Hz),
3.13 (1H, ddd, J 4.5, 7.0 and 11.0 Hz), 3.66 (3H, s), 5.98 (1H,
d, J 15.6 Hz), 6.79 (1H, dd, J 10.4 and 15.6 Hz), 7.42–7.59
(3H, m), 7.95–7.99 (2H, m); dC (100 MHz, CDCl3) 15.6
(CH2), 26.5 (CH), 26.6 (CH), 51.4 (CH3), 121.9 (CH),
128.1 (CH), 128.6 (CH), 133.0 (CH), 138.0 (CH), 146.0
(CH), 166.1 (C), 196.0 (C); m/z (CI) 231 (MH+) 248
(MNH+4); HRMS (CI) [MH+], found: 231.1016. C14H15O3 re-
quires 231.1021 (1.6 ppm error).
inseparable mixture of cyclopropane isomers (3.2:1), Rf
0.21 (petrol–EtOAc, 6:1); nmax (film) 2980, 2954, 1735,
1679, 1597, 1449, 1372, 1353, 1302, 1211, 1175, 1059,
1020 cmꢂ1; major isomer: dH (400 MHz, CDCl3) 1.28 (3H,
t, J 7.3 Hz), 1.30–1.32 (1H, m), 2.72 (1H, d, J 5.8 Hz), 3.75
(3H, s), 3.77–3.78 (1H, m), 4.19–4.24 (2H, m), 7.48–7.53
(3H, m), 8.09–8.12 (2H, m); minor isomer: dH (400 MHz,
CDCl3) 2.78 (1H, dd, J 5.2 and 9.8 Hz), 3.00 (1H, app t, J
5.5 Hz), 3.28 (1H, dd, J 5.5 and 9.8 Hz), 3.58 (3H, s),
7.51–7.60 (3H, m), 7.92–7.97 (2H, m) (the remaining signals
were obscured by the major isomer); dC (100 MHz, CDCl3)
14.1 (CH3), 29.1 (CH), 29.9 (CH), 30.0 (CH), 52.5 (CH3),
61.6 (CH2), 128.4 (CH), 128.7 (CH), 133.8 (CH), 136.3
(C), 168.0 (C), 168.4 (C), 194.9 (C); m/z (CI) 277 (MH+);
HRMS (CI) [MH+], found: 277.1077. C15H17O5 requires
277.1076 (ꢂ0.5 ppm error).
6.3.6. 2-((E)-2-Methoxycarbonyl-propenyl)-cyclopropane-
carboxylic acid ethyl 10f. Using the above procedure
for 10c (but with phosphorane 3c for 18 h), the title com-
pound 10f was prepared in 56% yield as a colourless oil as
an inseparable mixture (trans/cis w7:1), Rf 0.34 (petrol–
Et2O, 3:1); nmax (film) 2950, 1719, 1710, 1648, 1437, 1412,
1349, 1311, 1263, 1252, 1200, 1180, 1104, 1037 cmꢂ1; dH
(400 MHz, CDCl3) 1.05 (1H, ddd, J 4.3, 5.8 and 9.0 Hz),
1.22 (3H, d, J 7.0 Hz), 1.49 (1H, ddd, J 4.3, 5.5 and
9.4 Hz), 1.77 (1H, ddd, J 3.7, 5.5 and 9.0 Hz), 1.90 (3H, d,
J 1.5 Hz), 2.15 (1H, dddd, J 3.7, 5.8, 9.4 and 11.0 Hz), 3.67
(3H, s), 4.10 (2H, J 7.0 Hz), 6.06 (1H, dd, J 1.5 and
11.0 Hz); dC (100 MHz, CDCl3) 12.6 (CH3), 14.1 (CH3),
16.3 (CH2), 21.9 (CH), 22.6 (CH), 51.6 (CH3), 60.8 (CH2),
127.8 (C), 142.0 (CH), 168.0 (C), 172.7 (C); m/z (CI) 213
(MH+) 230 (MNH+4); HRMS (CI) [MH+], found: 230.1392.
C11H20NO4 requires 230.1391 (0.2 ppm error).
6.3.9. 2-Benzoyl-3-cyano-cyclopropanecarboxylic acid
ethyl ester 15b. Using the above procedure for 10c (but
for 3 h), the title compound 15b was prepared in 80% yield
as a yellow oil as a mixture of cyclopropane isomers (3.8:1),
m/z (CI) 261 (MNH+4); HRMS (CI) [MH+], found: 261.1240.
C14H17N2O3 requires 261.1239 (ꢂ0.1 ppm error). These
isomers could be partially separated by chromatography
(petrol–EtOAc, 4:1) giving major isomer: Rf 0.21 (petrol–
EtOAc, 4:1); nmax (film) 3062, 2984, 2247, 1734, 1678,
1597, 1450, 1372, 1346, 1295, 1201, 1186, 1014 cmꢂ1; dH
(400 MHz, CDCl3) 1.33 (3H, t, J 7.0 Hz), 2.56 (1H, dd, J
5.5 and 8.9 Hz), 2.66 (1H, dd, J 5.5 and 8.9 Hz), 3.74 (1H,
app t, J 5.5 Hz), 4.30 (2H, q, J 7.0 Hz), 7.51–7.55 (2H, m),
7.65–7.68 (1H, m), 8.01–8.03 (2H, m); dC (100 MHz,
CDCl3) 14.1 (CH3), 28.4 (CH), 28.5 (CH), 29.3 (CH), 62.4
(CH2), 115.8 (C), 128.6 (CH), 129.0 (CH), 134.5 (CH),
135.5 (C), 167.0 (C), 192.6 (C); minor isomer: Rf 0.18
(petrol–EtOAc, 4:1); nmax (film) 3050, 2983, 2246, 1729,
1672, 1596, 1449, 1368, 1350, 1296, 1199, 1180,
1011 cmꢂ1; dH (400 MHz, CDCl3) 1.32 (3H, t, J 7.3 Hz),
2.55 (1H, dd, J 5.5 and 8.8 Hz), 3.03 (1H, app t, J 5.5 Hz),
3.52 (1H, dd, J 5.5 and 8.8 Hz), 4.22–4.29 (2H, m), 7.52–
7.66 (3H, m), 8.04–8.05 (2H, m); dC (100 MHz, CDCl3)
14.0 (CH3), 27.4 (CH), 29.2 (CH), 29.3 (CH), 62.4 (CH2),
115.3 (C), 128.6 (CH), 129.1 (CH), 134.3 (CH), 135.9 (C),
168.7 (C), 190.9 (C).
6.3.7. Ethyl 2-(tert-butyldimethylsilanyloxymethyl)-2-(2-
methoxycarbonylethenyl)-cyclopropanecarboxylate
10g. Using the above procedure for 10c (but with phosphor-
ane 3a for 18 h), the title compound 10g was prepared in
64% yield as a colourless oil as an inseparable mixture of
cis/trans cyclopropane isomers (trans/E:cis/E w1.8:1), Rf
0.40 (petrol–EtOAc, 4:1); nmax (film) 2954, 2931, 2858,
1727, 1650, 1259, 1213, 1178, 1094, 838, 778 cmꢂ1; dH
(400 MHz, CDCl3) trans: 0.00 (3H, s, SiMe), 0.04 (3H, s,
SiMe), 0.83 (9H, s, SiCMe3), 1.21–1.26 (3H, m,
CO2CH2CH3), 1.26–1.30 (1H, m), 1.48–1.53 (1H, m), 1.94
(1H, dd, J 8.0 and 6.4 Hz), 3.71 (3H, s, OMe), 3.75 (1H, d,
J 11.0 Hz), 4.02 (1H, d, J 11.0 Hz), 4.04–4.20 (2H, m,
CO2CH2CH3), 5.97 (1H, d, J 15.6 Hz), 6.63 (1H, d,
J 15.6 Hz); cis: 0.04 (3H, s, SiMe), 0.05 (3H, s, SiMe),
0.85 (9H, s, SiCMe3), 1.26–1.30 (3H, m, CO2CH2CH3),
1.42 (1H, dd, J 4.0 and 8.2 Hz), 1.41–1.50 (1 H, m), 2.14
(1 H, dd, J 8.2 and 5.2 Hz), 3.70 (3H, s, OMe), 3.72 (1H,
d, J 10.4 Hz), 3.82 (1H, d, J 10.4 Hz), 4.04–4.20 (2H, m,
CO2CH2CH3), 5.89 (1H, d, J 16.5 Hz), 6.63 (1 H, d,
J 16.5 Hz); dC (100 MHz, CDCl3) trans: ꢂ5.4 (CH3), 14.3
(CH3), 18.2 (C), 18.3 (CH), 25.9 (CH3), 26.0 (CH), 33.6
(C), 51.6 (CH3), 61.0 (CH2), 61.6 (CH2), 119.3 (CH),
151.2 (CH), 167.2 (C), 170.6 (C); cis: ꢂ5.4 (CH3), ꢂ5.3
(CH3), 14.3 (CH3), 18.3 (C), 19.9 (CH2), 25.8 (CH), 25.9
(CH3), 32.3 (C), 51.6 (CH3), 61.0 (CH2), 63.4 (CH2),
120.5 (CH), 147.2 (CH), 166.9 (C), 171.2 (C); m/z (CI)
343 (MH+); HRMS (CI) [MH+], found: 343.1940.
C17H31O5Si requires 343.1941 (0.1 ppm error).
6.3.10. 2-Benzoyl-3-(methoxy-methyl-carbamoyl)-cyclo-
propanecarboxylic acid ethyl ester 15c. Using the above
procedure for 10c (but with phosphorane 3d for 4 h), the title
compound 15c was prepared in 50% yield as a yellow oil as
an inseparable mixture of cyclopropane isomers (2.2:1), Rf
0.26 (petrol–EtOAc, 3:2); nmax (film) 2980, 2940, 1732,
1686, 1655, 1597, 1449, 1411, 1381, 1335, 1277, 1220,
1183, 1010 cmꢂ1; dH (400 MHz, CDCl3) major isomer:
1.07 (3H, t, J 7.0 Hz), 2.79 (1H, dd, J 5.5 and 10.0 Hz),
3.03 (1H, app t, J 5.5 Hz), 3.25 (3H, s), 3.29 (1H, dd, J 5.5
and 10.0 Hz), 3.83 (3H, s), 4.02 (2H, q, J 7.0 Hz), 7.45–
7.50 (3H, m), 7.95–8.00 (2H, m); minor isomer: 1.30 (3H,
t, J 7.0 Hz), 3.21 (3H, s), 3.71 (3H, s), 4.22 (2H, q, J
7.0 Hz), 7.56–7.58 (3H, m), 8.06–8.11 (2H, m) (the remain-
ing signals were obscured by the major isomer); dC
(100 MHz, CDCl3) major isomer 13.9 (CH3), 23.2 (CH),
29.9 (CH), 32.6 (CH), 32.7 (CH3), 61.2 (CH2), 62.1 (CH3),
128.4 (CH), 128.7 (CH), 133.5 (CH), 136.4 (C), 168.2 (C),
169.7 (C), 192.8 (C); minor isomer 14.1 (CH3), 25.4 (CH),
6.3.8. 3-Benzoyl-cyclopropane-1,2-dicarboxylic acid 1-
ethyl ester 2-methyl ester 15a. Using the above procedure
for 10c (but with phosphorane 3a for 4 h), the title compound
15a was prepared in 83% yield as a colourless oil as an