Radical Hydro‐Ethoxycarbonyldifluoromethylation of Alkenes with BrCF2CO2Et

Abstract The difluoromethylene (CF₂) group, valued for its unique electronic and steric properties, plays a critical role in pharmaceutical and agrochemical design, as exemplified by drugs like lubiprostone, which requires ethyl 2,2‐difluorohexanoate as a key intermediate for its synthesis. Consequently, developing efficient methods to incorporate the ethoxycarbonyldifluoromethyl group into alkanes is highly desirable. Herein, we describe a mild, versatile, and efficient radical hydro‐ethoxycarbonyldifluoromethylation of alkenes with BrCF 2 CO 2 Et. This process is applicable to both unactivated alkyl alkenes and active aryl alkenes. The protocol is characterized by mild reaction conditions, the absence of expensive reagents, and the elimination of transition metals.