Triphenylphosphine Catalyzed Michael Addition of Oximes onto Activated Olefins [1]

Abstract

A new reaction condition for Michael addition of oximes onto activated olefins has been discovered using a catalytic amount of triphenylphosphine. This is a first and milder alternative to classical base (hydroxide, alkoxide) catalyzed Michael addition of oximes. Various aldoximes 1a-h and ketoximes 2a-c (Figure [1] ) were reacted with different Michael acceptors such as ethyl acrylate, acrylonitrile, phenyl vinyl sulfone, methyl vinyl ketone, and 1-nitrocyclohex-1-ene to obtain the corresponding Michael adducts. About 35 different examples were attempted (Table [1] and Scheme [1] ); except in six cases where reactions did not produce desired products, yields varied from good to excellent. Reactions without triphenylphosphine did not proceed. A plausible mechanism of catalytic action in the present reactions is proposed (Figure [2] ).

Michael additions - oximes - alkenes - phosphorus - catalysis

References

1

DRL Publication No. 284.

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13

Oximes were prepared by reacting the corresponding carbonyl compounds with excess of hydroxylamine in methanol, either at r.t. or when required under heating (55 °C).