Stereochemical Control by an Ester Group or Olefin Ligand
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53.30, 63.40, 72.59, 79.89, 104.05, 126.82, 126.86, 126.87,
126.95, 128.58, 128.64, 143.98, 144.20, 167.14, 168.11; IR
(neat): n=3022, 2973, 2893, 1707, 1679, 1634, 1433, 1304,
1164, 1091, 1015 cmÀ1; HR-MS (ESI): m/z=389.1723, calcd.
for (M+Na)+: 389.1723.
(Z)-2,2,2-Trichloroethyl
2-[dihydro-4,4-diphenylfuran-
2(3H)-ylidene]-3-isopropoxybutanoate [(Z)-2i]: 1H NMR
(270 MHz, CDCl3): d=0.77 (d, J=6.2 Hz, 3H), 1.04 (d, J=
5.8 Hz, 3H), 1.28 (d, J=6.6 Hz, 3H), 3.31–3.40 (m, 1H),
3.51 (d, J=16.1 Hz, 1H), 3.80 (d, J=16.1 Hz, 1H), 4.69–4.91
(m, 5H), 7.19–7.34 (m, 10H); 13C NMR (67 MHz, CDCl3):
d=21.08, 21.76, 22.88, 43.60, 53.38, 68.20, 68.59, 73.70, 80.31,
95.62, 103.65, 126.85, 126.98, 128.64, 143.80, 144.04, 164.24,
171.40; IR (neat): n=3062, 2965, 2942, 1723, 1613, 1159,
1143, 1085, 1025, 971 cmÀ1; HR-MS (ESI): m/z=519.0863,
calcd. for (M+Na)+: 519.0867.
(E)-Methyl 3-ethoxy-2-[dihydro-4,4-diphenylfuran-2(3H)-
ylidene]butanoate [(E)-2e]: 1H NMR (500 MHz, CDCl3):
d=1.13 (t, J=6.8 Hz, 3H), 1.43 (d, J=6.4 Hz, 3H), 3.26–
3.37 (m, 2H), 3.71 (s, 3H), 3.77 (d, J=17.1 Hz, 1H), 3.84 (d,
J=17.1 Hz, 1H), 4.69 (q, J=6.4 Hz, 1H), 4.74 (d, J=9.0 Hz,
1H), 4.79 (d, J=9.0 Hz, 1H), 7.17–7.30 (m, 10H); 13C NMR
(125 MHz, CDCl3): d=15.33, 20.06, 44.92, 50.99, 53.52,
63.40, 70.56, 80.02, 105.42, 126.80, 126.85, 126.89, 128.54,
128.55, 144.27, 144.49, 168.72, 171.22; IR (neat): n=3060,
2972, 2893, 1696, 1623, 1281, 1092, 1066, 1027 cmÀ1; HR-MS
(ESI): m/z=389.1722, calcd. for (M+Na)+: 389.1723.
(E)-Ethyl 3-ethoxy-2-[dihydro-4,4-diphenylfuran-2(3H)-
ylidene]butanoate [(E)-2f]: 1H NMR (500 MHz, CDCl3):
d=1.14 (t, J=6.8 Hz, 3H), 1.28 (t, J=7.3 Hz, 3H), 1.45 (d,
J=6.4 Hz, 3H), 3.26–3.38 (m, 2H), 3.78 (d, J=17.1 Hz,
1H), 3.84 (d, J=17.1 Hz, 1H), 4.13–4.23 (m, 2H), 4.68–4.73
(m, 2H), 4.79 (d, J=9.0 Hz, 1H), 7.17–7.30 (m, 10H);
13C NMR (125 MHz, CDCl3): d=14.29, 15.27, 19.97, 44.90,
53.40, 59.57, 63.21, 70.57, 79.90, 105.54, 108.71, 126.71,
126.74, 126.77, 126.80, 128.44, 128.46, 144.22, 144.48, 168.11,
170.85; IR (neat): n=3084, 2970, 2882, 1679, 1613, 1264,
1093, 1065 cmÀ1; HR-MS (ESI): m/z=403.1878, calcd. for
(M+Na)+: 403.1880.
(Z)-2,2,2-Trichloroethyl
2-[dihydro-4,4-diphenylfuran-
2(3H)-ylidene]-3-isobutoxybutanoate [(Z)-2j]: 1H NMR
(270 MHz, CDCl3): d=0.72 (d, J=6.6 Hz, 3H), 0.78 (d, J=
6.6 Hz, 3H), 1.30 (d, J=6.6 Hz, 3H), 1.54–1.67 (m, 1H),
2.85 (d, J=6.6 Hz, 2H), 3.50 (d, J=16.3 Hz, 1H), 3.74 (d,
J=16.3 Hz, 1H), 4.54 (q, J=6.6 Hz, 1H), 4.75–4.90 (m,
4H), 7.18–7.33 (m, 10H); 13C NMR (67 MHz, CDCl3): d=
19.31, 19.38, 21.24, 28.26, 43.50, 53.38, 72.61, 73.68, 75.27,
80.29, 95.65, 103.08, 126.85, 128.62, 143.88, 144.01, 164.26,
170.87; IR (neat): n=3060, 2956, 2870, 1717, 1614, 1261,
1158, 1088, 1040, 961 cmÀ1; HR-MS (ESI): m/z=533.1026,
calcd. for (M+Na)+: 533.1024.
2,2,2-Trichloroethyl (2Z)-3-ethoxy-2-(2-oxaspiroACTHNUGRTNEUNG[4.5]dec-
1
3-ylidene)butanoate [(Z)-2k]: H NMR (600 MHz, CDCl3):
d=1.18 (t, J=7.0 Hz, 3H), 1.39 (d, J=6.6 Hz, 3H), 1.46–
1.52 (m, 10H), 2.69 (d, J=17.2 Hz, 1H), 2.91 (d, J=17.2 Hz,
1H), 3.32–3.37 (m, 1H), 3.46–3.51 (m, 1H), 4.08 (d, J=
8.8 Hz, 1H), 4.11 (d, J=8.8 Hz, 1H), 4.63 (q, J=6.6 Hz,
1H), 4.74 (d, J=12.0 Hz, 1H), 4.82 (d, J=12.0 Hz, 1H);
13C NMR (150 MHz, CDCl3): d=15.35, 21.43, 23.25, 23.33,
25.69, 34.18, 41.34, 42.79, 63.41, 72.16, 73.59, 81.44, 95.68,
101.61, 164.28, 173.23; IR (neat): n=2972, 2926, 2854, 1723,
1686, 1616, 1451, 1258, 1158, 1091, 1013 cmÀ1; HR-MS
(ESI): m/z=421.0710, calcd. for (M+Na)+: 421.0711.
(E)-4-Methoxyphenyl 3-ethoxy-2-[dihydro-4,4-diphenyl-
furan-2(3H)-ylidene]butanoate
[(E)-2g]:
1H NMR
(270 MHz, CDCl3): d=1.19 (t, J=7.0 Hz, 3H), 1.54 (d, J=
6.6 Hz, 3H), 3.32–3.50 (m, 2H), 3.78–3.95 (m, 5H), 4.77–
4.89 (m, 3H), 6.84–6.92 (m, 2H), 6.97–7.03 (m, 2H), 7.16–
7.32 (m, 10H); 13C NMR (67 MHz, CDCl3): d=15.44, 20.20,
45.29, 53.55, 55.53, 55.62, 63.50, 70.62, 70.72, 80.39, 104.99,
114.32, 122.67, 126.89, 128.62, 144.17, 144.40, 157.00, 167.34,
173.15; IR (neat): n=3059, 2971, 2896, 1705, 1620, 1505,
1191, 1079, 1021, 977 cmÀ1; HR-MS (ESI): m/z=481.1983,
calcd. for (M+Na)+ 481.1985.
(Z)-Phenyl 3-ethoxy-2-[dihydro-4,4-diphenylfuran-2(3H)-
ylidene]butanoate [(Z)-2h]: 1H NMR (600 MHz, CDCl3):
d=0.99 (t, J=7.0 Hz, 3H), 1.37 (d, J=6.7 Hz, 3H), 3.20 (m,
2H), 3.52 (d, J=16.1 Hz, 1H), 3.83 (d, J=16.1 Hz, 1H),
4.64 (q, J=6.7 Hz, 1H), 4.79 (d, J=9.1 Hz, 1H), 4.92 (d, J=
9.1 Hz, 1H), 7.13–7.37 (m, 15H); 13C NMR (150 MHz,
CDCl3): d=15.24, 21.49, 43.33, 53.41, 63.52, 72.57, 80.14,
103.51, 121.99, 126.83, 126.88, 128.66, 128.71, 129.13, 143.86,
144.12, 151.06, 164.92, 170.24; IR (neat): n=3059, 3037,
2972, 2927, 2862, 1718, 1611, 1589, 1488, 1160, 1151, 1132,
965 cmÀ1; anal. calcd. for C28H28O4: C 78.48, H 6.59, N 0.00;
found: C 78.26, H 6.57, N 0.00.
(E)-Phenyl 3-ethoxy-2-[dihydro-4,4-diphenylfuran-2(3H)-
ylidene]butanoate [(E)-2h]: 1H NMR (600 MHz, CDCl3):
d=1.19 (t, J=7.0 Hz, 3H), 1.55 (d, J=6.9 Hz, 3H), 3.37–
3.46 (m, 2H), 3.85 (d, J=17.5 Hz, 1H), 3.92 (d, J=17.5 Hz,
1H), 4.79–4.88 (m, 3H), 7.08–7.38 (m, 15H); 13C NMR
(150 MHz, CDCl3): d=15.47, 20.23, 45.36, 53.55, 63.55,
70.70, 80.45, 104.91, 122.00, 126.78, 126.88, 128.65, 128.67,
129.23, 144.13, 144.39, 150.92, 167.04, 173.47; IR (neat): n=
3057, 2973, 2870, 1698, 1613, 1596, 1492, 1277, 1202,
1024 cmÀ1; anal. calcd. for C28H28O4: C 78.48, H 6.59, N
0.00; found: C 78.52, H 6.57, N 0.00.
2,2,2-Trichloroethyl (2E)-3-ethoxy-2-(2-oxaspiroACTHNUGRTNEUNG[4.5]dec-
1
3-ylidene)butanoate [(E)-2k]: H NMR (600 MHz, CDCl3):
d=1.17 (t, J=7.0 Hz, 3H), 1.46–1.48 (m, 13H), 3.01 (d, J=
18.3 Hz, 1H), 3.06 (d, J=18.3 Hz, 1H), 3.34–3.45 (m, 2H),
4.01 (d, J=8.8 Hz, 1H), 4.06 (d, J=8.8 Hz, 1H), 4.72 (q, J=
6.8 Hz, 1H), 4.77 (d, J=12.0 Hz, 1H), 4.83 (d, J=12.0 Hz,
1H); 13C NMR (150 MHz, CDCl3): d=15.44, 19.91, 23.25,
23.36, 25.69, 34.56, 34.60, 41.46, 44.89, 63.44, 70.75, 73.89,
81.68, 95.65, 103.41, 166.33, 175.08; IR (neat): n=2971,
2926, 2856, 1703, 1614, 1451, 1371, 1274, 1086, 1009,
911 cmÀ1; HR-MS (ESI): m/z=421.0712, calcd. for (M+
Na)+: 421.0711.
(Z)-2,2,2-Trichloroethyl 3-ethoxy-2-[dihydro-4,4-dimethyl-
furan-2(3H)-ylidene]butanoate
[(Z)-2l]:
1H NMR
(270 MHz, CDCl3): d=1.16–1.20 (m, 9H), 1.39 (d, J=
6.6 Hz, 3H), 2.69 (d, J=16.9 Hz, 1H), 2.86 (d, J=16.9 Hz,
1H), 3.29–3.56 (m, 2H), 4.03 (s, 2H), 4.61 (q, J=6.6 Hz,
1H), 4.76 (d, J=12.1 Hz, 1H), 4.84 (d, J=12.1 Hz, 1H);
13C NMR (67 MHz, CDCl3): d=15.30, 21.45, 24.79, 37.35,
45.35, 63.40, 72.25, 73.63, 83.07, 95.69, 101.96, 164.26, 173.05;
IR (neat): n=2969, 2875, 1725, 1687, 1618, 1371, 1303, 1261,
1158, 1088, 1011, 965 cmÀ1; HRMS (ESI): m/z=381.0395,
calcd. for (M+Na)+: 381.0398.
(E)-2,2,2-Trichloroethyl 3-ethoxy-2-[dihydro-4,4-dimethyl-
furan-2(3H)-ylidene]butanoate
(270 MHz, CDCl3): d=1.12–1.20 (m, 9H), 1.48 (d, J=
6.6 Hz, 3H), 2.95 (d, J=17.9 Hz, 1H), 3.03 (d, J=17.9 Hz,
[(E)-2l]:
1H NMR
Adv. Synth. Catal. 2009, 351, 1089 – 1100
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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