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在烯炔金（I）催化环化反应中间体的结构研究中：反式稠合双环[5.1.0]辛烷的形成作为案例研究。

On the Structure of Intermediates in Enyne Gold(I)-Catalyzed Cyclizations: Formation of trans-Fused Bicyclo[5.1.0]octanes as a Case Study.

机构信息

Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.

Departament de Química Orgànica i Analítica, Universitat Rovira i Virgili (URV), C/ Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.

出版信息

Chemistry. 2020 Dec 1;26(67):15738-15745. doi: 10.1002/chem.202004237. Epub 2020 Nov 19.

DOI:10.1002/chem.202004237
PMID:33155306
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7756441/
Abstract

The nature of cyclopropyl gold(I) carbene-type intermediates has been reexamined as part of a mechanistic study on the formation of cis- or trans-fused bicyclo[5.1.0]octanes in a gold(I)-catalyzed cascade reaction. Benchmark of DFT methods together with QTAIM theory and NBO analysis confirms the formation of distinct intermediates with carbenic or carbocationic structures in the cycloisomerizations of enynes.

摘要

作为金（I）催化级联反应中环合形成顺式或反式稠合双环[5.1.0]辛烷的机理研究的一部分，重新考察了环丙基金（I）卡宾型中间体的性质。DFT 方法的基准测试以及 QTAIM 理论和 NBO 分析证实了在烯炔的环异构化中存在具有卡宾或碳正离子结构的不同中间体的形成。

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