Photocatalytic 1,2-aminoformylation of olefins with bifunctional oxime esters

Here, we disclose a metal-free photochemical strategy for the single-step synthesis of β-amido acetals through the regioselective difunctionalization of alkenes using bifunctional oxime esters. This method operates under mild conditions (visible light irradiation, room temperature) and exhibits broad substrate compatibility, including styrenes, acrylonitriles, and bioactive alkenes, with isolated yields ranging from 53% to 83%. The success of this approach hinges on the design of oxime esters as dual radical precursors, which facilitate the simultaneous formation of C–C and C–N bonds via a triplet energy transfer pathway. Scalability was demonstrated via a continuous flow reaction, affording the product in 80% yield (2.10 g) and mechanistic studies confirm a radical-mediated process. This metal-free, energy-efficient protocol aligns with sustainable chemistry principles by avoiding toxic metal catalysts.