Visible-Light-Induced Radical Cascade Cross-Coupling via C(sp3)-H Activation and C-N/N-O Cleavage: Feasible Access to Methylenebisamide Derivatives

Here we report facile and manipulable access to methylenebisamide derivatives via visible-light-driven radical cascade processes incorporating C(sp3)-H activation and C-N/ N-O cleavage. Mechanistic studies reveal that a traditional Ir-catalyzed photoredox pathway and a novel copper-induced complex-photolysis pathway are both involved, contributing to activating the inert N-methoxyamides and rendering the valuable bisamides. This approach exhibits many advantages, including mild reaction conditions, broad scope and functional group tolerance, and competitive step economy. Given the mechanistic plenitude and operational simplicity, we believe this package deal paves a promising way for the synthesis of valuable nitrogen-containing molecules.

Automated summary

We report a convenient and manipulable synthesis of methylenebisamide derivatives through visible-light-driven radical cascade reactions incorporating C(sp3)-H activation and C-N/ N-O cleavage. Mechanistic studies reveal the involvement of both a traditional Ir-catalyzed photoredox pathway and a novel copper-induced complex-photolysis pathway, enabling the activation of inert N-methoxyamides and the synthesis of valuable bisamides. This approach offers many advantages, including mild reaction conditions, broad scope and functional group tolerance, and competitive step economy. With its mechanistic plenitude and operational simplicity, we believe this method paves a promising way for the synthesis of valuable nitrogen-containing molecules.