The mechanistic puzzle of transition-metal-catalyzed skeletal rearrangements of enynes

被引：199

作者：

Nieto-Oberhuber, Cristina ^{[1
]}

Lopez, Salome ^{[1
]}

Jimenez-Nunez, Eloisa ^{[1
]}

Echavarren, Antonio M. ^{[1
]}

机构：

[1] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2006年 / 12卷 / 23期

关键词：

alkynes; cyclization; density functional calculations; gold; rearrangement;

D O I：

10.1002/chem.200600174

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Three pathways actually compete in metal-catalyzed cyclizations of enynes in which the metal selectively activates the alkyne: an endocyclic process and two exo-cyclizations, one proceeding by anti attack of the alkene and a second one resulting in a syn addition. Although cyclobutenes may be formed in transition-metal-catalyzed cyclization of some enynes, particularly, 1,7-enynes. these compounds are not necessarily the intermediates in the skeletal rearrangement. Cyclobutenes are formed by ring expansion of syn-cyclopropyl metal-carbenes formed in the syn pathway.

引用

页码：5916 / 5923

页数：8

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