A Unified Photocatalytic Strategy for Fluoroalkylated and Cyanated α-Tertiary Amino/Glycolic Acids via a Radical-Polar Cascade.

A redox-neutral, metal-free, visible-light-driven strategy is developed for constructing fluoroalkylated and cyanated α-tertiary amino acids (ATAAs) via a radical migration-mediated radical-polar cascade. This mild protocol generates multifunctional α-carbonyl carbocations, which are trapped by nitriles to afford diverse ATAAs with a broad scope. The synthetic utility is demonstrated through the late-stage modification of bioactive molecules. Remarkably, trapping the carbocations with HO provides fluoroalkylated and cyanated α-tertiary glycolic acids (ATGAs) in good yields, thus offering a powerful tool for privileged pharmaceutical scaffold development.