Deuteriodifluoromethylation and gem‐Difluoroalkenylation of Aldehydes Using ClCF₂H in Continuous Flow

The deuteriodifluoromethyl group (CF 2 D) represents a challenging functional group due to difficult deuterium incorporation and unavailability of precursor reagents. Herein, we report the use of chlorodifluoromethane (ClCF 2 H) gas in the continuous flow deuteriodifluoromethylation and gem ‐difluoroalkenylation of aldehydes. Mechanistic studies revealed that the difluorinated oxaphosphetane (OPA) intermediate can proceed via alkaline hydrolysis in the presence of D 2 O to provide α‐deuteriodifluoromethylated benzyl alcohols or undergo a retro [2+2] cycloaddition under thermal conditions to provide the gem ‐difluoroalkenylated product.