Catalytic tert-alkylation of enamides via C-C bond cleavage under photoredox conditions.

Efficient C-C bond cleavage is recognized as a persistent challenge in the field of synthetic methodology. In this study, we found that tertiary alkyl radicals are smoothly formed from tertiary alkylated dienones (BHT adducts) via SET, using PDI as a photocatalyst. Resulting tert-alkyl radicals could be applied to the tert-alkylation of enamides. The driving force of this C-C bond cleavage reaction is the mesolytic cleavage of the BHT adducts. The mechanistic study revealed that PDI anion radical is the key active species during the catalytic cycle.