烯酮[2+2]环加成反应中的动力学拆分：一项实验与理论研究。

Kinetic resolution in the [2+2] cycloaddition of ketenes: an experimental and theoretical study.

作者信息

Rullière Pauline, Carret Sébastien, Milet Anne, Poisson Jean-François

机构信息

Université Joseph Fourier, CNRS, Département de Chimie Moléculaire, SERCO, UMR 5250, ICMG FR-2607, BP 53, 38041 Grenoble CEDEX 9 (France), Fax: (+33) 4-76-63-57-54.

出版信息

Chemistry. 2015 Mar 2;21(10):3876-81. doi: 10.1002/chem.201405393. Epub 2015 Jan 29.

DOI:10.1002/chem.201405393

PMID:25640298

Abstract

The kinetic resolution of Z and E olefins by [2+2] cycloaddition with ketenes allows the isolation of pure E olefin, as well as the synthesis of pure cis-cyclobutanones, starting from Z/E mixtures. A computational rationale for this kinetic difference is reported. The obtained difference of energy of activation matches with the experimental results.

摘要

通过与烯酮进行[2+2]环加成反应对Z型和E型烯烃进行动力学拆分，能够从Z/E混合物中分离出纯E型烯烃，同时还能合成纯的顺式环丁酮。本文报道了这种动力学差异的计算原理。所得到的活化能差异与实验结果相符。