Recent Progress in Asymmetric Oxidative Radical–Polar Crossover Reactions

Radical–polar crossover (RPCO) has emerged as a powerful synthetic strategy, using the complementary properties of both radical and classical polar chemistry. Radical–polar crossover, especially its oxidative radical–polar crossover (ORPCO), facilitates efficient asymmetric synthesis by converting radical intermediates to carbocations, which allow the formation of enantioselective bonds. This ability to form CC, CO, and CN bonds underlines its significant potential for late–stage functionalization of complex molecules and for diversification of medicinal products. This review summarizes the recent developments in the asymmetric ORPCO domain, including catalytic strategies, transformation mechanisms, and current characteristics. Research into new catalytic strategies and asymmetric bonding paradigms is an important frontier of future research, with the potential to significantly increase the scale and usefulness of ORPCO reactions.