Photoinduced Copper‐Catalyzed Enantioselective Allylic C(sp3)−H Oxidation of Acyclic 1‐Aryl‐2‐alkyl Alkenes as Limiting Substrates

Herein, we disclose a simple copper‐catalyzed method for enantioselective allylic C(sp3)−H oxidation of unsymmetrical acyclic alkenes, specifically 1‐aryl‐2‐alkyl alkenes. The C−H substrates are used in limiting amounts, and the products are obtained with high enantioselectivity, E/Z‐selectivity, and regioselectivity. The method exhibits broad functional group tolerance, and E/Z‐alkene mixtures are suitable C−H substrates. The transformation is enabled by light irradiation, which sustains the enantioselective copper catalysis by photoinduced oxidant homolysis. The first copper‐catalyzed method for highly enantioselective allylic C−H oxidation of acyclic alkenes is reported. Using this method, mixtures of E/Z‐alkenes undergo photoinduced allylic oxidation with high enantioselectivity, E/Z‐selectivity, and regioselectivity. Importantly, the C−H substrates are used as limiting reagents. The method displays good functional group tolerance and is amenable to late‐stage C−H functionalization.