PAPER
Deconjugation of Unsaturated Fused-Cyclopentenone Phosphonates
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(d, JPH = 25.0 Hz, 1 H), 2.69 (dd, J = 11.0 Hz, J = 18.0 Hz, 1 H),
2.30 (dd, J = 6.0 Hz, J = 19.0 Hz, 1 H), 1.76–1.73 (m, 2 H), 1.48–
1.42 (m, 2 H), 1.37–1.27 (m, 14 H), 0.89 (t, J = 7.0 Hz, 3 H).
31P NMR (202.4 MHz): d = 22.9.
HRMS (ESI, +): m/z [M + H]+ calcd for C22H40O5P: 415.26079;
found: 415.26077.
13C NMR (125.7 MHz): d = 211.2 (d, 2JPC = 4.0 Hz), 105.9, 105.8,
2
2
73.0, 62.8 (d, JPC = 6.0 Hz), 62.2 (d, JPC = 6.0 Hz), 49.2 (d,
1JPC = 130.0 Hz), 43.8, 38.9, 37.6, 31.5, 29.6, 29.0, 23.4, 22.4, 16.1
(d, 3JPC = 5.0 Hz), 13.9.
Diethyl (3-Benzyl-5-oxo-4,5,6,6a-tetrahydro-1H-cyclopen-
ta[c]furan-4-yl)phosphonate (3h)
Yield: 0.2461 g (14%); colorless oil.
31P NMR (202.4 MHz): d = 22.9.
HRMS (ESI, +): m/z [M + H]+ calcd for C18H32O5P: 359.19819;
IR (neat): 2922, 2851, 1727, 1647, 1601, 1453, 1239, 1144, 1022,
965 cm–1.
found: 359.19818.
1H NMR (500 MHz): d = 7.33–7.24 (m, 5 H), 4.24 (t, J = 8.0 Hz, 1
H), 4.14–4.01 (m, 4 H), 3.61 (dd, J = 3.5 Hz, J = 9.0 Hz, 1 H), 3.30
(s, 2 H), 3.10–2.99 (m, 2 H), 2.64 (dd, J = 10.0 Hz, JPH = 20.0 Hz,
1 H), 2.15 (dd, J = 6.0 Hz, J = 18.0 Hz, 1 H), 1.34 (t, J = 7.0 Hz, 3
H), 1.30 (t, J = 7.0 Hz, 3 H).
Diethyl (3-Nonyl-5-oxo-4,5,6,6a-tetrahydro-1H-cyclopen-
ta[c]furan-4-yl)phosphonate (3e)
Yield: 0.4826 g (25%); colorless oil.
IR (neat): 2923, 2853, 1745, 1649, 1466, 1232, 1161, 1095, 1016,
968 cm–1.
31P NMR (202.4 MHz): d = 22.9.
1H NMR (500 MHz): d = 4.24 (t, J = 9.0 Hz, 1 H), 4.19–4.11 (m, 4
H), 3.77 (dd, J = 4.0 Hz, J = 8.0 Hz, 1 H), 3.20–3.11 (m, 1 H), 3.03
(d, JPH = 25.0 Hz, 1 H), 2.67 (dd, J = 10.0 Hz, J = 19.0 Hz, 1 H),
2.28 (dd, J = 7.0 Hz, J = 19.0 Hz, 1 H), 1.74–1.71 (m, 2 H), 1.47–
1.39 (m, 2 H), 1.38–1.19 (m, 18 H), 0.87 (t, J = 7.0 Hz, 3 H).
Supporting Information for this article is available online at
Acknowledgment
13C NMR (125.7 MHz): d = 211.0 (d, 2JPC = 4.0 Hz), 106.1, 106.0,
This study was supported by research grant number 01797 from the
Chief Scientist Office of the Israeli Ministry of Health. This work is
included in the PhD thesis of D.M. as a partial requirement of the
Hebrew University of Jerusalem.
2
2
73.2, 62.9 (d, JPC = 6.0 Hz), 62.4 (d, JPC = 6.0 Hz), 49.4 (d,
1JPC = 129.0 Hz), 43.9, 39.2, 37.7, 31.8, 29.7, 29.4, 29.2, 23.5, 22.5,
16.2 (d, 3JPC = 5.0 Hz), 13.9.
31P NMR (202.4 MHz): d = 23.0.
HRMS (ESI, +): m/z [M + H]+ calcd for C20H36O5P: 387.22949;
found: 387.22952.
References
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Diethyl (3-Decyl-5-oxo-4,5,6,6a-tetrahydro-1H-cyclopen-
ta[c]furan-4-yl)phosphonate (3f)
Yield: 0.5601 g (28%); colorless oil.
(3) Cristau, H. J.; Gazc, M. B.; Mbianda, X. Y.; Geze, A.
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M. Mini Rev. Org. Chem. 2005, 2, 91.
IR (neat): 2923, 2853, 1746, 1647, 1457, 1257, 1160, 1097, 1017,
972 cm–1.
1H NMR (500 MHz): d = 4.24 (t, J = 8.5 Hz, 1 H), 4.20–4.11 (m, 4
H), 3.77 (dd, J = 4.0 Hz, J = 8.0 Hz, 1 H), 3.20–3.11 (m, 1 H), 3.03
(d, JPH = 25.0 Hz, 1 H), 2.68 (dd, J = 10.0 Hz, J = 18.0 Hz, 1 H),
2.29 (dd, J = 6.0 Hz, J = 19.0 Hz, 1 H), 1.75–1.71 (m, 2 H), 1.45–
1.40 (m, 2 H), 1.37–1.22 (m, 20 H), 0.88 (t, J = 7.0 Hz, 3 H).
13C NMR (125.7 MHz): d = 211.1 (d, 2JPC = 5.0 Hz), 106.1, 106.0,
2
2
73.2, 62.9 (d, JPC = 6.0 Hz), 62.4 (d, JPC = 6.0 Hz), 49.4 (d,
1JPC = 130.0 Hz), 43.9, 39.2, 37.7, 31.8, 29.54, 29.51, 29.48, 29.40,
29.2, 23.5, 22.6, 16.2 (d, 3JPC = 3.0 Hz), 14.0.
31P NMR (202.4 MHz): d = 22.9.
HRMS (ESI, +): m/z [M + H]+ calcd for C21H38O5P: 401.24514;
found: 401.24518.
(10) Baum, O.; Quntar, A. A.; Demitsky, V. M.; Srebnik, M.
Tetrahedron 2004, 60, 1359.
(11) Quntar, A. A.; Baum, O.; Shibli, A.; Dembitsky, V. M.;
Srebnik, M. Angew. Chem. Int. Ed. 2003, 42, 4777.
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67, 3769.
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(19) Quntar, A. A.; Rosenthal, D.; Srebnik, M. Tetrahedron
2006, 62, 5995.
Diethyl (5-Oxo-3-undecyl-4,5,6,6a-tetrahydro-1H-cyclopen-
ta[c]furan-4-yl)phosphonate (3g)
Yield: 0.6011 g (29%); colorless oil.
IR (neat): 2922, 2852, 1746, 1649, 1466, 1232, 1160, 1096, 1018,
969 cm–1.
1H NMR (500 MHz): d = 4.27 (t, J = 8.0 Hz, 1 H), 4.21–4.14 (m, 4
H), 3.79 (dd, J = 4.0 Hz, J = 8.0 Hz, 1 H), 3.22–3.13 (m, 1 H), 3.04
(d, JPH = 24.0 Hz, 1 H), 2.70 (dd, J = 11.0 Hz, J = 19.0 Hz, 1 H),
2.30 (dd, J = 6.0 Hz, J = 19.0 Hz, 1 H), 1.76–1.73 (m, 2 H), 1.48–
1.42 (m, 2 H), 1.38–1.23 (m, 22 H), 0.89 (t, J = 7.0 Hz, 3 H).
13C NMR (125.7 MHz): d = 211.3 (d, 2JPC = 4.0 Hz), 106.0, 105.9,
2
2
73.0, 62.9 (d, JPC = 6.0 Hz), 62.3 (d, JPC = 6.0 Hz), 49.3 (d,
1JPC = 129.0 Hz), 43.8, 39.0, 37.6, 31.7, 29.7, 29.5, 29.4, 29.1, 23.5,
22.5, 16.1 (d, 3JPC = 5.0 Hz), 13.9.
© Thieme Stuttgart · New York
Synthesis 2012, 44, 1258–1262