Reaction Pathway of the Conjugate Addition of Lithium Organocuprate Clusters to Acrolein
Reaction Pathway of the Conjugate Addition of Lithium Organocuprate Clusters to Acrolein
复制标题
有机铜酸锂团簇与丙烯醛共轭加成的反应路径
DOI：
10.1021/ja964209h
复制
发表时间：
1997
影响因子：
15
通讯作者：
K. Morokuma
中科院分区：
文献类型：
--
作者：
E. Nakamura;S. Mori;K. Morokuma
用杂化密度泛函B3LYP方法研究了铜酸盐簇合物(Me2CuLi)2的甲基转移到丙烯醛(甲基的共轭加成)的反应途径。测定了反应势面上的所有中间体和过渡结构，以及反应C-−-C成键阶段附近本征反应坐标上的结构。除了先前提出的两个物种，锂/羰基配合物(CPLi)和具有闭合铜酸盐结构的铜/烯烃配合物(CPCL)外，一种新的具有开放铜酸盐结构的铜/烯烃配合物(CPOP)被表征并被证明是通过C-−-C键形成(TS)的TS直接导致共轭加成产物(PD)的中间体。反应的总路径可以被认为，一方面是通过还原消除铜(III)物种而形成C-−C键，另一方面是通过铜辅助的Meli的1，4-加成。目前的研究成果主要集中在三个方面。
The reaction pathway of transfer of a methyl group of a cuprate cluster (Me2CuLi)2 to acrolein (conjugate addition of the methyl group) has been studied with the hybrid density functional B3LYP method. All intermediates and transition structures (TSs) on the potential surface of the reaction as well as the structures on the intrinsic reaction coordinate near the C−C bond forming stage of the reaction have been determined. In addition to two previously proposed species, a lithium/carbonyl coordination complex (CPli) and a copper/olefin complex retaining a closed cuprate structure (CPcl), a new copper/olefin complex with an open cuprate structure (CPop) was characterized and proven to be an intermediate directly leading to the conjugate addition product (PD) via a TS of C−C bond formation (TS). The overall pathway of the reaction can be viewed, in one way, as C−C bond formation via reductive elimination of a Cu(III) species and, in another, as a 1,4-addition of MeLi assisted by copper. The present studies r...