Light-Driven Enantioselective Organocatalytic ?-Benzylation of Enals.

ABSTRACT: A photochemical organocatalytic strategy for the direct enantioselective ?-benzylation of ?,?-unsaturated aldehydes is reported. The chemistry capitalizes upon the light-triggered enolization of 2-alkyl-benzophenones to afford hydroxy-o-quinodinomethanes. These fleeting intermediates are stereoselectively intercepted by chiral iminium ions, transiently formed upon condensation of a secondary amine catalyst with enals. Density functional theory (DFT) studies provided an explanation for why the reaction proceeds through an unconventional Michael-type addition manifold, instead of a classical cycloaddition mechanism and subsequent ring-opening.

SUBMITTER: Dell'Amico L 

PROVIDER: S-EPMC5412672 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature