Nature of the Intermediates in Gold(I)-Catalyzed Cyclizations of 1,5-Enynes

被引：70

作者：

Lopez-Carrillo, Veronica ^{[1
]}

Huguet, Nuria ^{[1
]}

Mosquera, Angeles ^{[1
]}

Echavarren, Antonio M. ^{[1
,2
]}

机构：

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

[2] Univ Rovira & Virgili, Dept Quim Analit & Quim Organ, Tarragona 43007, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 39期

关键词：

cyclization; density functional theory; enynes; gold; reaction mechanisms; GOLD-CATALYZED CYCLOISOMERIZATION; AU(I)-CATALYZED CYCLOISOMERIZATIONS; STEREOSELECTIVE-SYNTHESIS; PLATINUM CATALYSIS; EFFICIENT; ALKENES; ENYNES; CYCLOPROPANATION; ACCESS; CARBOCYCLIZATION;

D O I：

10.1002/chem.201101749

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The carbene or carbocationic nature of the intermediates in the gold-catalyzed cycloisomerization of 1,5-enynes can be revealed, depending on the ligands on the gold catalysts. Gold complexes with highly electron-donating ligands promote reactions that proceed via intermediates with carbene-like character, leading to products with a bicyclo[3.1.0]hexene skeleton. The intermediate cyclopropyl endo-gold carbenes formed in this cyclization have been trapped, for the first time, to give biscyclopropane derivatives in a reaction that proceeds in a concerted fashion, according to DFT calculations.

引用

页码：10972 / 10978

页数：7

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