Photoinduced Radical-Polar Crossover Enabling Three-Component Carbooxygenation of Arylalkenes

An efficient photoinduced radical-polar crossover strategy is described for the three-component carbooxygenation of arylalkenes, enabling their concomitant cyanomethylation/carbonylmethylation and esterification. This method facilitates the direct incorporation of cyanomethyl/carbonylmethyl and ester groups into readily available olefins using α-bromo nitriles/α-bromo esters and carboxylic acids as key reagents. The reaction proceeds under mild conditions at room temperature, exhibiting good functional group tolerance, a broad substrate scope, and high atom economy. Notably, despite the relatively weak nucleophilicity of carboxylic acids, they can be directly incorporated into this photoinduced radical-polar crossover transformation. Moreover, this protocol is also applicable to other nucleophiles, including alcohols, water, and aromatic amines, thereby significantly enhancing its synthetic versatility. This work offers a practical and versatile approach to constructing multifunctionalized molecules.