Noninnocent Counterion Effect on the Rearrangements of Cationic Intermediates in a Gold(I)-Catalyzed Alkenylsilylation Reaction

被引：28

作者：

Zhou, Tao ^{[1
]}

Xu, Liang ^{[1
]}

Xia, Yuanzhi ^{[1
]}

机构：

[1] Wenzhou Univ, Coll Chem & Mat Engn, Wenzhou 325035, Peoples R China

来源：

ORGANIC LETTERS | 2013年 / 15卷 / 23期

基金：

中国国家自然科学基金;

关键词：

GOLD-CATALYZED CYCLOISOMERIZATION; PTCL2-MEDIATED CYCLOISOMERIZATION; POLYFUNCTIONALIZED 1,6-ENYNES; MECHANISTIC INSIGHTS; DENSITY FUNCTIONALS; HYDROAMINATION; ARYLSILYLATION; CYCLOADDITIONS; CYCLIZATION; ALLYLATION;

D O I：

10.1021/ol4029644

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A mechanistic DFT study of the gold(I)-catalyzed alkenylsilylation reaction of a silyl-tethered 1,6-enyne system is reported. A novel pathway involving bistriflimide counterion-assisted rearrangements of carbocation and silyl cation intermediates corroborates the experimental observations. The results suggest the important role of the counterion in modulating the reactivity of cationic intermediates in gold catalysis.

引用

页码：6074 / 6077

页数：4

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