- Scope and Mechanism in Palladium-Catalyzed Isomerizations of Highly Substituted Allylic, Homoallylic and Alkenyl Alcohols
Evgeny Larionov, Luqing Lin, Laure Guénée, Clément Mazet*
J. Am. Chem. Soc. 2014, 136, 16882-16894
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, 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.
open archive unige:43003
Editor’s version DOI: 10.1021/ja508736u