Diarylfluoromethyl sulfonium salts are efficient fluoromethylene transfer reagents equivalent to fluorocarbene, which is difficult to access. This was demonstrated by the development of a monofluorinated Johnson–Corey–Chaykovsky reaction with ketones and aldehydes, delivering uncommon 2‐unsubstituted fluoroepoxides. This is the first evidence for the feasibility of sulfur fluoromethylylide and its action as a reaction intermediate.

A fluorocyclopropanation of double activated alkenes with a diarylfluoromethylsulfonium reagent is an efficient approach to obtain a range of monofluorocyclopropane derivatives.

The synthesis of five-membered rings using fluoromethylene transfer chemistry is an attractive method for building fluorinated products of high value. This work demonstrates for the first time that one-fluorine-one-carbon modification...

An investigation of the properties and reactivity of fluoromethylsulfonium salts resulted in the redesign of the reagents for fluoromethylene transfer chemistry. The model reaction, fluorocyclopropanation of nitrostyrene, turned out to be a suitable platform for the discovery of more streamlined fluoromethylene transfer reagents. The incorporation of halides on one aryl ring increased the reactivity, and 2,4-dimethyl substitution on the other aryl ring provided a balance between the reactivity/crystallinity of the reagent as well as the atom economy. The utility of new reagents was demonstrated by the development of an efficient fluorocyclopropanation protocol to access a range of monofluorinated cyclopropane derivatives.