关于齐默尔曼双π-甲烷重排反应机理的反应电子通量观点

Reaction Electronic Flux Perspective on the Mechanism of the Zimmerman Di-π-methane Rearrangement.

作者信息

Matute Ricardo A, Pérez Patricia, Chamorro Eduardo, Villegas-Escobar Nery, Cortés-Arriagada Diego, Herrera Barbara, Gutiérrez-Oliva Soledad, Toro-Labbé Alejandro

机构信息

Laboratorio de Química Teórica Computacional (QTC), Facultad de Química , Pontificia Universidad Católica de Chile , Avenida Vicuña Mackenna 4860 , 7820436 , Santiago , Chile.

Division of Chemistry and Chemical Engineering , California Institute of Technology , Pasadena , California 91125 , United States.

出版信息

J Org Chem. 2018 Jun 1;83(11):5969-5974. doi: 10.1021/acs.joc.8b00499. Epub 2018 Mar 14.

DOI:10.1021/acs.joc.8b00499

PMID:29486121

Abstract

The reaction electronic flux (REF) offers a powerful tool in the analysis of reaction mechanisms. Noteworthy, the relationship between aromaticity and REF can eventually reveal subtle electronic events associated with reactivity in aromatic systems. In this work, this relationship was studied for the triplet Zimmerman di-π-methane rearrangement. The aromaticity loss and gain taking place during the reaction is well acquainted by the REF, thus shedding light on the electronic nature of reactions involving dibenzobarrelenes.

摘要

反应电子通量（REF）为反应机理分析提供了一个强大的工具。值得注意的是，芳香性与REF之间的关系最终能够揭示与芳香体系中反应活性相关的微妙电子事件。在这项工作中，针对三线态齐默尔曼双-π-甲烷重排研究了这种关系。REF清楚地显示了反应过程中芳香性的丧失和增加，从而阐明了涉及二苯并桶烯的反应的电子本质。