Electrocatalytic Polarity Inversion of Azlactones: Access to α‐Quaternary Amino Acids with Electron‐Rich SOMOphiles

ABSTRACT The use of azlactones as nucleophiles is a well‐established strategy to access α‐quaternary amino acids. Herein, we present an electrocatalytic approach that reverses the natural polarity of azlactones. Indirect oxidation of the azlactone enolate, using triarylamine electrocatalysts, generates an electrophilic radical intermediate that couples with a variety of electron‐rich SOMOphiles. This strategy enables Csp 3 ─Csp 2 and Csp 3 ─Csp 3 bond formation at the α‐position of the azlactone, providing access to arylated, β‐oxoalkylated, alkenylated, and allylated quaternary amino acid derivatives.