CF3S,CF3 and HCF2 groups have been identified as valuable functionalities for drug development.Despite significant accomplishments in the trifluoromethylthiolation,trifluoromethylation and difluoromethylation reactions,directly converting common functional groups into CF3S,CF3 or HCF2 groups is still highly desirable.Described here is the dehydroxylative trifluoromethylthiolation,trifluoromethylation and difluoromethylation of alcohols promoted by a R3P/ICH2CH21 system.All of these dehydroxylative reactions were achieved under mild conditions via the activation of the hydroxyl group by the R3P/ICH2CH2I system.A wide substrate scope and good functional group tolerance were observed.