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

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 Csp3─Csp2 and Csp3─Csp3 bond formation at the α-position of the azlactone, providing access to arylated, β-oxoalkylated, alkenylated, and allylated quaternary amino acid derivatives.