Synthesis of Chloro(phenyl)trifluoromethyliodane and Catalyst-Free Electrophilic Trifluoromethylations

Abstract

The present work deals with a challenge in the synthesis of aryltrifluoromethyliodanes (ArICF₃X) and develops a direct route to PhICF₃Cl via a simple ligand-exchange reaction of PhI(OCOCF₃)₂, Me₃SiCF₃, and NaCl for the first time. The I-Cl bond length in PhICF₃Cl supports its iodonium character, which enables an enhanced CF₃-transfer capability in electrophilic S-, O-, N-, and C-trifluoromethylations as well as in catalyst-free trifluoromethylation-cyclizations of arylisonitriles.