Photoredox‐Catalyzed Generation of Tertiary Anions from Primary Amines via a Radical Polar Crossover

Abstract

AbstractA method for the generation of tertiary carbanions via a deaminative radical‐polar crossover is reported using redox active imines from α‐tertiary primary amines. A variety of benzylic amines and amino esters can be used in this approach, with the latter engaging in a novel “aza‐Reformatsky” reaction. Electronic trends correlate the stability of the resulting carbanion with reaction efficiency. The anions can be trapped with different electrophiles including aldehydes, ketones, imines, Michael acceptors, and H2O/D2O. Selective anion formation can be achieved in the presence of another equivalent or more acidic C−H bond in both an inter‐ and intramolecular fashion. Mechanistic studies suggest the intermediacy of a discrete carbanion intermediate.