Generation and Trapping of Cyclopentenylidene Gold Species: Four Pathways to Polycyclic Compounds

被引：199

作者：

Lemiere, Gilles ^{[1
]}

Gandon, Vincent ^{[1
]}

Cariou, Kevin ^{[1
]}

Hours, Alexandra ^{[1
]}

Fukuyama, Takahide ^{[1
]}

Dhimane, Anne-Lise ^{[1
]}

Fensterbank, Louis ^{[1
]}

Malacria, Max ^{[1
]}

机构：

[1] Univ Paris 06, Inst Chim Mol FR 2769, CNRS, Chim Organ Lab,UMR 7611, F-75252 Paris 05, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 08期

关键词：

DIELS-ALDER REACTIONS; ASYMMETRIC TOTAL-SYNTHESIS; MOLECULAR-ORBITAL METHODS; BENT ACYCLIC ALLENE; GAUSSIAN-TYPE BASIS; CATALYZED CYCLOISOMERIZATION; SKELETAL REARRANGEMENT; C-C; GOLD(I)-CATALYZED CYCLOISOMERIZATION; PTCL2-CATALYZED CYCLOISOMERIZATIONS;

D O I：

10.1021/ja808872u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cyclopentenylidene gold complexes can easily be formed from vinyl allenes through a Nazarov-like mechanism. Such carbenes; may transform in four different ways into polycyclic frameworks: electrophilic cyclopropanation, C-H insertion, C-C migration, or proton shift. We have studied the selectivity of these different pathways and used our findings for the expedient preparation of valuable complex molecules. An application to the total synthesis of a natural product, Delta(9(12))-capnellene, is presented. DFT computations were carried out to shed light on the mechanisms.

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页码：2993 / 3006

页数：14

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