Electrocatalytic Polarity Inversion of Azlactones: Access to α-Quaternary Amino Acids with Electron-Rich Coupling Partners

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 couple 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 azlactone, providing access to arylated, β-oxoalkylated, alkenylated and allylated quaternary amino acid derivatives.