Catalytic Dicyanative [4+2] Cycloaddition Triggered by Cyanopalladation of Conjugated Enynes under Aerobic Conditions

A palladium-catalyzed dicyanative [4+2] cycloaddition reaction using dienynes with TMSCN under aerobic conditions is described. This new reaction triggered by the cyanopalladation of terminal alkynes includes regioselective direct cyanation to C−C triple bonds by TMSCN to give π-allyl Pd intermediat...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2010-04, Vol.132 (13), p.4522-4523
Main Authors: Arai, Shigeru, Koike, Yuka, Hada, Hirohiko, Nishida, Atsushi
Format: Article
Language:English
Subjects:
Alkynes - chemistry
Catalysis
Cyclization
Molecular Structure
Nitriles - chemical synthesis
Nitriles - chemistry
Oxygen - chemistry
Stereoisomerism
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Summary:A palladium-catalyzed dicyanative [4+2] cycloaddition reaction using dienynes with TMSCN under aerobic conditions is described. This new reaction triggered by the cyanopalladation of terminal alkynes includes regioselective direct cyanation to C−C triple bonds by TMSCN to give π-allyl Pd intermediates, which promotes 5-exo followed by 6-endo cyclization. This protocol enables (1) the formation of four C−C bonds through one operation, (2) the construction of highly functionalized cyclohexene rings, and (3) the generation of five contiguous stereogenic centers in one operation. The intermolecular cycloaddition reaction between a conjugated enyne and methyl acrylate also proceeded in a regioselective fashion to give multifunctionalized carbocycles.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja910451j