Synthesis 2007(8): 1225-1229  
DOI: 10.1055/s-2007-965982
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 3-(Phosphorylmethyl)cycloalkenones by Forced Conjugate Addition of α-Phosphonate Carbanions to Cyclic Enones

Marian Mikolajczyk*, Wieslawa Perlikowska
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Department of Heteroorganic Chemistry, Sienkiewicza 112, 90-363 Lodz, Poland
Fax: +48(42)6847126; e-Mail: marmikol@bilbo.cbmm.lodz.pl;
Further Information

Publication History

Received 25 October 2006
Publication Date:
12 March 2007 (online)

Abstract

Cycloalkenones were found to react with α-lithiated diethyl (phenylselanyl)methylphosphonate preferentially or exclusively at the carbonyl group giving 1,2-adducts. When complexes of cycloalkenones with aluminum tris(2,6-diphenylphenoxide) were used for this reaction, regioselective 1,4-addition was observed. Upon oxidation the thus-formed 1,4-adducts gave the corresponding 3-(phosphorylmethyl)cycloalk-2-enones. An alternative approach to the latter compounds involved 1,4-addition of diethyl lithiomethylphosphonate to 2-sulfinylcycloalk-2-enones followed by sulfoxide elimination.

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17

The starting cyclohexenyl sulfoxide was prepared by oxidation of the corresponding sulfide according to ref. 16. However, our product was crystalline and not an oil as reported. For full spectroscopic and analytical data, see the experimental part.