The deuteriodifluoromethyl group (CF2D) represents a challenging functional group due to difficult deuterium incorporation and unavailability of precursor reagents.
Herein, we report the use of chlorodifluoromethane (ClCF2H) 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 D2O to provide α‐deuteriodifluoromethylated benzyl alcohols or undergo a retro [2+2] cycloaddition under thermal conditions to provide the gem ‐difluoroalkenylated product.