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

CuCN和N-苄基苯磺酰胺的混合物催化二烷基锌或二芳基锌（Cu：Zn = 1：200 ~ 1：10000）与α，β-不饱和酮的1，4-加成反应，经水处理后，以近定量的产率得到相应的β-取代酮。一系列具有-s-顺式或s-反式几何构型的环状烯酮以及构象柔性的无环烯酮可用作底物。乙基比甲基和苯基更容易迁移。CuOTf、CuO-t-C_4，H_9和均三甲苯基铜可代替CuCN。原位形成的烯醇化烷基锌，在水性处理之前，进一步经历与醛的羟醛缩合反应或Pd（0）辅助的与乙酸烯丙酯的偶联，产生区域控制的邻位碳缩合产物。一个催化循环的基础上提出的动力学研究和结构分析的烯醇化锌产品的NMR和分子量测量。

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.