A general efficient one‐pot synthesis of S‐perfluoroalkylated NH‐sulfoximines from sulfides has been developed using phenyliodine diacetate (PIDA) and ammonium carbamate. Remarkable rate enhancement with trifluoroethanol was observed, presumably due to H‐bonding effects. These mild and metal‐free conditions are compatible with ‐CH2F, ‐CFCl2, ‐CF2H, ‐CF2Br, ‐C4F9, and ‐CF3 groups, in both the alkyl‐ and aryl series. Based on a 19F NMR analysis, a λ6‐acetoxysulfanenitrile intermediate was proposed.

A method for the trifluoromethylation of ortho‐hydroxycinnamic esters was developed to achieve the regioselective synthesis of 3‐trifluoromethylated coumarins. The reaction was performed by using the Togni reagent as the CF3 source under mild conditions and showed good functional‐ group tolerance. The scope of this copper‐mediated method was further expanded to the synthesis of 3‐trifluoromethylated carbostyrils starting from ortho‐aminocinnamic derivatives. Interestingly, a sequential one‐pot synthesis of 3‐trifluoromethylated coumarins starting from salicylaldehydes was further developed. The mechanism of this cascade reaction was explored, and a radical pathway was found to be consistent with the obtained results.