Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti-Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

The involvement of a catalytic metal vinylidene species was proposed for the first time in 1986 to explain the regioselective formation of vinyl carbamates directly from terminal alkynes, carbon dioxide, and amines. Since this initial report, various metal vinylidenes and allenylidenes, which are ke...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2006-03, Vol.45 (14), p.2176-2203
Main Authors: Bruneau, Christian, Dixneuf, Pierre H.
Format: Article
Language:English
Subjects:
alkene metathesis
allenylidenes
anti-Markovnikov addition
Catalysis
Chemical Sciences
homogeneous catalysis
vinylidenes
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Summary:The involvement of a catalytic metal vinylidene species was proposed for the first time in 1986 to explain the regioselective formation of vinyl carbamates directly from terminal alkynes, carbon dioxide, and amines. Since this initial report, various metal vinylidenes and allenylidenes, which are key activation intermediates, have proved extremely useful for many alkyne transformations. They have contributed to the rational design of new catalytic reactions. This 20th anniversary is a suitable occasion to present the advancement of organometallic vinylidenes and allenylidenes in catalysis. Versatile key intermediate metal vinylidenes and allenylidenes participate in numerous catalytic processes such as alkene metathesis, coupling reactions, and anti‐Markovnikov additions to alkynes. The formation of a metal vinylidene intermediate in a catalytic reaction (see scheme) was first reported 20 years ago, and much development in the field has since taken place.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200501391