N-tosylhydrazones as acceptors for nucleophilic alkyl radicals in photoredox catalysis: A short case study on possible side reactions

We report the attempted development of a photoredox-catalyzed α-C–H alkylation reaction of aliphatic amine derivatives, using N-tosylhydrazones as radical alkylating partners. The original intention was to intercept α-aminoalkyl radical intermediates with N-tosylhydrazones, followed by the expulsion of a sulfonyl radical by β-scission to generate N-H diazene species. Facile denitrogenation of these intermediates would remove all traces of the hydrazone moiety and provide a net C–H alkylation process. However, our plans were derailed by issues with the low reactivity of N-tosylhydrazones toward intermolecular capture by nucleophilic radicals, and several unexpected side reactions. Our findings, though unsuccessful, do serve to identify challenges for future researchers attempting to develop similar transformations.