Photoinduced Copper-Catalyzed Aminoalkylation of Amino-Pendant Olefins

The combination of photo and copper catalysts has emergedas anovel paradigm in organic catalysis, which provides access to theacceleration of chemical synthesis. Herein, we describe an aminoalkylationof amino-dependent olefins with maleimides through a cooperative photo/coppercatalytic system. In this report, the strategy allows the generationof a broad complex of functionalized nitrogenous molecules includingoxazolidinones, 2-pyrrolidones, imidazolidinones, thiazolidinones,pyridines, and piperidines in the absence of an external photosensitizerand base. The approach is achieved through a photoinduced Cu(I)/Cu(II)/Cu(III)complex species of nitrogen nucleophiles, intermolecular radical addition,and hydrogen atom transfer (HAT) processes. The plausible mechanismis investigated by a series of control experiments and theoreticaltests, including radical scavenging experiments, deuterium labelingexperiments, ultraviolet-visible absorption, and cyclic voltammetry(CV) tests.

Automated summary

The combination of photo and copper catalysts can accelerate chemical synthesis and achieve aminoalkylation reactions. This strategy allows the generation of a broad range of functionalized nitrogenous molecules in the absence of an external photosensitizer and base. The reaction proceeds through a photoinduced complex species of nitrogen nucleophiles, intermolecular radical addition, and hydrogen atom transfer processes, as investigated by control experiments and theoretical tests.