Generation and Utility of Tertiary α-Aminoorganolithium Reagents

A general approach to tertiary α-aminoorganolithium reagents by reductive lithiation of α-aminonitriles has been developed. This class of organolithium nucleophiles reacts efficiently with carbonyl electrophiles or in intramolecular cyclizations with tethered phosphate leaving groups. Transmetalation can be used to produce α-aminoorganocuprate reagents that react with alkyl halide electrophiles and in 1,4-additions with enones. These methods establish a new approach for the synthesis of quaternary centers adjacent to nitrogen.