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

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.