Electrochemical Activation of α-Carbonyl Alkoxyamines for Direct Nucleophilic Substitution

The reactivity and synthetic utility of TEMPO-derived alkoxyamines as functional handles remains insufficiently explored. This report interrogates the factors governing the stereospecific substitution of electroactivated TEMPO-derived α-carbonyl alkoxyamines. Concurrent with direct electrolysis, electroanalytical studies and theoretical calculations provided a complementary platform by which one could predict the efficacy for substrates to undergo desired substitution using benzoic acid or <i>N</i>-sulfonyl carbamate nucleophiles.