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

The present work deals with a challenge in the synthesis of aryltrifluoromethyliodanes (ArICF3 X) and develops a direct route to PhICF3 Cl via a simple ligand-exchange reaction of PhI(OCOCF3 )2 , Me3 SiCF3 , and NaCl for the first time. The I-Cl bond length in PhICF3 Cl 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.