Rh-Catalyzed Desymmetrization of α-Quaternary Centers by Isomerization-Hydroacylation.

ABSTRACT: We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.

SUBMITTER: Park JW 

PROVIDER: S-EPMC4618402 | biostudies-literature | 2015 Aug

REPOSITORIES: biostudies-literature