Theoretical studies of nucleophilic additions of monomeric and dimeric organometallics
Theoretical studies of nucleophilic additions of monomeric and dimeric organometallics
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单体和二聚有机金属亲核加成的理论研究
DOI：
10.1039/ft9949001789
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发表时间：
1994
期刊：
影响因子：
--
通讯作者：
K. Morokuma
中科院分区：
文献类型：
--
作者：
Masaharu Nakamura;E. Nakamura;N. Koga;K. Morokuma
用从头算方法研究了金属有机物种与烯烃和羰基化合物的亲核加成反应途径。在第一部分中，立体化学的环丙烯的carbometrides已检查实验和理论模型系统开发的实验立体选择性的理由。在第二部分中，已经研究了甲基锂二聚体与醛的反应，以获得对二聚体物种在有机化学中，特别是在不对称羰基加成中的作用的基本理解。比较了立体选择性羰基加成反应与烯烃的羰基化反应的原理。
The reaction pathways of nucleophilic addition of organometallic species to alkenes and carbonyl compounds have been studied by ab initio theoretical calculations. In the first part, the stereochemistry of the carbometallation of cyclopropene has been examined experimentally and theoretically for a model system to develop a rationale for the experimental stereoselectivity. In the second part, the reaction of a methyllithium dimer with aldehydes has been studied to obtain a basic understanding of the role of dimeric species in organic chemistry, especially, in asymmetric carbonyl additions. The principle of stereoselective carbonyl addition is compared with that of carbometallation of alkenes.