One pot synthesis of mono- or bi-cyclic phosphiranes and phosphirenes

Abstract

Treatment of phospholene oxide 1, vinylphosphine oxide 11 or alkynylphosphine oxide 14 with [Cp₂Zr] 2 followed by addition of a chlorophosphine leads to various phosphiranes and phosphirenes.

References

1. F. Mathey, Chem. Rev., 1990, 90, 997.
2. N. Cénac, A. Chrostowska, J.-M. Sotiropoulos, B. Donnadieu, A. Igau, G. Pfister-Guillouzo and J.-P. Majoral, Organometallics, 1997, 16, 4551; L. Dupuis, N. Pirio, P. Meunier, A. Igau, B. Donnadieu and J.-P. Majoral, Angew. Chem., Int. Ed. Engl., 1997, 36, 987; M. Zablocka, A. Igau, B. Donnadieu, J.-P. Majoral and A. Skowronska, Chem. Commun., 1997, 1239 and references cited therein.
3. For recent reviews on zirconocene, see for example: Y. Hanzawa, H. Ito and T. Taguchi, Synlett, 1995, 299; A. Ohff, S. Pulst, C. Lefeber, N. Peulecke, P. Arndt, V. V. Burkalov and U. Rosenthal, Synlett, 1996, 111 references cited therein.
4. A dimeric form cannot be totally ruled out for 4, 12 and 15.
5. M. Zablocka, A. Igau, J.-P. Majoral and K. M. Pietrusiewicz, Organometallics, 1993, 12, 603.
6. Selected data for 4: δ_C(CDCl₃) 41.0 (d, J_PC 96.0, PCHZr), 58.1 (d, J_PC 13.5, CHZr), 33.2 (d, J_PC 19.2, CH₂), 29.0 (d, J_PC 73.6, PCH₂). For 5a: δ_C 26.3 [dd, J_P(O)C 16.5, J_PC 38.0, P(O)CHP], 24.7 (d, J_PC 51.0, CHP), 24.3 [d, J_PC 71.8, P(O)CH₂], 22.5 (d, J_PC 7.5, CH₂). For 8: δ_C 21.6 (s, CH₃), 22.4 (d, J_PC 12.2, ZrCH₂), 35.6 (s, ZrCHCH₂), 39.4 (d, J_PC 18.2, PCH₂CH₂), 40.0 (d, J_PC 18.7, PCH₂), 41.8 (d, J_PC 3.3, ZrCH). For 13: δ_C 28.2 (dd, J_PC 29.0, J_PC= 13.0, CH), 25.5 (dd, J_PC 13.5, J_PC 2.9, CH₂). For 15: δ_C 153.5 [d, ¹J_PC 59.7, P(O)CZr], 148.3 (d, J_PC 6.1, ZrCPh). For 16a: δ_C 145.0 [dd, J_PC 53.2, J_P(O)C 10.2, P(O)C=], 139.6 (dd, J_PC 62.6, J_P(O)C 2.7, PCPh).
7. A. Mahieu, Y. Miquel, A. Igau, B. Donnadieu and J.-P. Majoral, Organometallics, 1997, 16, 3086.
8. Compound 9 was isolated as two isomers (PMe₃/Et cis or trans)(refs. 11, 12). According to NMR spectroscopy only the trans isomer for 8 was formed. However, these data do not allow the determination of the position of the C=C π-system in the phospholane ring with respect to the zirconacyclopropane fragment.
9. Full desulfurisation occurs when 1 equiv. of 1b is treated with 2 equiv. of 2.
10. See for example: M. Zablocka, F. Boutonnet, A. Igau, F. Dahan, J.-P. Majoral and K. M. Pietrusiewicz, Angew. Chem., Int. Ed. Engl., 1993, 32, 1735; M. Zablocka, A. Igau, N. Cénac, B. Donnadieu, F. Dahan, J.-P. Majoral and K. M. Pietrusiewicz, J. Am. Chem. Soc., 1995, 117, 8083.
11. S. L. Buchwald, B. T. Watson and J. C. Huffman, J. Am. Chem. Soc., 1987, 109, 2544.
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