Gold-Catalyzed Reactions via Cyclopropyl Gold Carbene-like Intermediates

Cycloisomerizations of 1,n-enynes catalyzed by gold­(I) proceed via electrophilic species with a highly distorted cyclopropyl gold­(I) carbene-like structure, which can react with different nucleophiles to form a wide variety of products by attack at the cyclopropane or the carbene carbons. Particul...

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Bibliographic Details
Published in:Journal of organic chemistry 2015-08, Vol.80 (15), p.7321-7332
Main Authors: Dorel, Ruth, Echavarren, Antonio M
Format: Article
Language:English
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Summary:Cycloisomerizations of 1,n-enynes catalyzed by gold­(I) proceed via electrophilic species with a highly distorted cyclopropyl gold­(I) carbene-like structure, which can react with different nucleophiles to form a wide variety of products by attack at the cyclopropane or the carbene carbons. Particularly important are reactions in which the gold­(I) carbene reacts with alkenes to form cyclopropanes either intra- or intermolecularly. In the absence of nucleophiles, 1,n-enynes lead to a variety of cycloisomerized products including those resulting from skeletal rearrangements. Reactions proceeding through cyclopropyl gold­(I) carbene-like intermediates are ideally suited for the bioinspired synthesis of terpenoid natural products by the selective activation of the alkyne in highly functionalized enynes or polyenynes.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.5b01106