Togni‐II Reagent Mediated Selective Hydrotrifluoromethylation and Hydrothiolation of Alkenes†

Main observation and conclusion Based on the redox reactions of Togni‐II reagent and thiols, a thiol‐tuned selective functionalization of unactivated olefins was disclosed. In combination with aryl thiols, stoichiometric amount of Togni‐II reagent prompted a hydrotrifluoromethylation of alkenes, in which, aryl thiols played as reductant and hydrogen source; while by utilization of alkyl thiols, catalytic amount of Togni‐II reagent initiated thiol‐ene and thiol‐yne reactions. The reported applications are characterized by their operational simplicity and wide functional group tolerance.