A simple and efficient method for the synthesis of α‐branched amines through formal oxidative C–H functionalization is reported. A commercially available quinone organocatalyst is employed to promote the aerobic oxidation of primary amines to the corresponding N‐protected imines, which are then trapped in situ with an appropriate nucleophile to give access to versatile functionalized amines in good to excellent yields (70–90 %).

A new method for amino acid homologation by way of formal C–C bond functionalization is reported. This method utilizes a 2-step/1-pot protocol to convert α-amino acids to their corresponding N-protected β-amino esters through quinone-catalyzed oxidative decarboxylation/in situ Mukaiyama–Mannich addition. The scope and limitations of this chemistry are presented. This methodology provides an alternative to the classical Arndt–Eistert homologation for accessing β-amino acid derivatives. The resulting N-protected amine products can be easily deprotected to afford the corresponding free amines.

A new method for imine synthesis by way of quinone-catalyzed oxidative deformylation of 1,2-amino alcohols is reported. A wide range of readily accessible amino alcohols and primary amines can be reacted to provide N-protected imine products. The methodology presented provides a novel organocatalytic approach for imine synthesis and demonstrates the synthetic versatility of quinone-catalyzed oxidative C–C bond cleavage.