Metal-Free Visible-Light Induced Oxidative Cleavage of C(sp 3 )-C, and C(sp 3 )-N Bonds of Nitriles, Alcohols, and Amines.

Selective cleavage of unstrained (sp 3 ) C-C/ C-N bonds under mild conditions is highly challenging due to the higher bond dissociation energy. A visible light mediated metal-free oxidative dehomologation of aryl acetonitriles, primary alcohols and diols to carboxylic acids via organophotocatalyzed C(sp 3 )-CN, C(sp 3 )-C(OH) bond cleavage is reported. Notably, this methodology was further extended towards selective synthesis of aldehydes via deamination of both primary as well as secondary amines. This mild protocol features wide array of substrate variation with excellent functional group tolerance, preparative-scale synthesis, and operational simplicity. Possible mechanisms for these transformations were demonstrated through a series of control experiments.