Mechanistic Insight into the Nickel-Catalyzed Intermolecular [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate with Alkynes: DFT Calculations

被引：9

作者：

An, Yanhong ^{[1
]}

Cheng, Caihong ^{[1
]}

Pan, Ben ^{[1
]}

Wang, Zhihong ^{[1
]}

机构：

[1] Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2012年 / 2012卷 / 21期

基金：

中国国家自然科学基金; 高等学校博士学科点专项科研基金;

关键词：

Cyclization; Reaction mechanisms; Density functional calculations; Nickel; EFFECTIVE CORE POTENTIALS; COENZYME-M REDUCTASE; MOLECULAR CALCULATIONS; 4+3 CYCLOADDITION; COMPLEXES; ABSORPTION; REACTIVITY; OLEFINS; PATH; SET;

D O I：

10.1002/ejoc.201200363

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

DFT investigations were employed to explore the complete reaction mechanism of the nickel-catalyzed [3+2+2] cocyclization of ethyl cyclopropylideneacetate and alkynes. The lowest-energy pathway involves the formation of a p complex between the methylenecyclopropane moiety and the nickel atom and occurs through a sequence of ring-opening and ring-closing reactions with CC bond formation as the rate-determining step. The crucial conversion of nickelacycloheptadiene to an eight-membered nickelacycle was suggested to happen in a stepwise mechanism instead of the previously proposed cyclopropenylbutenyl rearrangement.

引用

页码：3911 / 3915

页数：5

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