Scope and Mechanism in Palladium-Catalyzed Isomerizations of Highly Substituted Allylic, Homoallylic, and Alkenyl Alcohols

Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the pr...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-12, Vol.136 (48), p.16882-16894
Main Authors: Larionov, Evgeny, Lin, Luqing, Guénée, Laure, Mazet, Clément
Format: Article
Language:English
Subjects:
Alcohols - chemistry
Catalysis
Ketones - chemical synthesis
Ketones - chemistry
Molecular Structure
Organometallic Compounds - chemistry
Palladium - chemistry
Stereoisomerism
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Summary:Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja508736u