Electro‐Organocatalysis: Enantioselective α‐Alkylation of Aldehydes

Abstract The asymmetric organocatalyzed α‐alkylation of aldehydes via a cationic radical enamine intermediate was performed under environmentally benign electro‐oxidation conditions without the use of chemical oxidants. To promote the desired α‐alkylation reaction of aldehydes, various aldehydes with xanthene or cycloheptatriene groups were exposed to electro‐organocatalytic conditions to afford optically active α‐substituted aldehydes (α‐alkylated aldehydes) in good yield. A reaction mechanism involving the cationic radical enamine was proposed based on the cyclic voltammetry (CV) results, DFT calculations, and control experiments.