1,4-Addition of Diorganozincs to α,β-Unsaturated Ketones Catalyzed by a Copper(I)-SuIfonamide Combined System.

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A mixture of CuCN and N-benzylbenzenesulfnamide catalyzes the 1,4-addition of dialkylzincs or diarylzincs(Cu : Zn = 1 : 200 to l : 10000)to α,β-unsaturated ketones to give, after aqueous workup, the corresponding β-substituted ketones in nearly quantitative yields. A range to cyclic enones having-s-cis or s-trans geometries as well as conformationally flexible acyclic enones are usable as substrates. The ethyl group migrates more readily than the methy and phenyl groups. CuOTf, CuO-t-C_4,H_9, and mesitylcopper can be used in place of CuCN. The in situ-formed alkylzinc enolate, prior to aqueous workup, further undergoes an aldol reaction with aldehydes or Pd(0)-assisted coupling with allyl acetate, resulting in regio-controlled, vicinal carbacondensation products. A catalytic cycle is proposed on the basis of a kinetic study and a structural analysis of the zinc enolate product by NMR and molecular weight measurements.