Catalytic 1,4-Rhodium(III) Migration Enables 1,3-Enynes to Function as One-Carbon Oxidative Annulation Partners in CH Functionalizations

1,3‐Enynes containing allylic hydrogens cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double CH activation, involving a hi...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-09, Vol.53 (37), p.9931-9935
Main Authors: Burns, David J., Lam, Hon Wai
Format: Article
Language:English
Subjects:
Activation
Alkynes
Catalysis
Catalysts
Chemical reactions
Communications
CH functionalization
enyne
Hydrogen atoms
Migration
Organic chemistry
oxidation
rhodium
Transformations
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Summary:1,3‐Enynes containing allylic hydrogens cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double CH activation, involving a hitherto rare example of the 1,4‐migration of a RhIII species. This phenomenon is general across a variety of substrates, and provides a diverse range of heterocyclic products. When two become one: 1,3‐Enynes containing allylic hydrogen atoms cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double CH activation, involving a hitherto rare example of the 1,4‐migration of a RhIII species.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201406072