In the presence of copper thiocyanate, sodium thiocyanate and the inexpensive, easy-to-use trifluoromethylating reagent Me 3 Si-CF 3 , diazonium salts are smoothly converted into the corresponding aryl trifluoromethyl thioethers. Combined with diazotisation, this convenient and inexpensive method allows the straightforward synthesis of aryl or heteroaryl trifluoromethyl thioethers from the corresponding anilines.

Copper capabilities: Diazonium salts are converted into the corresponding trifluoromethyl derivatives in the presence of a trifluoromethyl–copper complex generated in situ from CuSCN and the inexpensive, easy‐to‐use trifluoromethylating reagent Me3Si‐CF3 (see scheme). This Sandmeyer‐type reaction allows the straightforward synthesis of trifluoromethylated arenes and heteroarenes from the corresponding amines.

By using silver complexes with bulky ligands such as DavePhos or N-heterocyclic carbenes, propargylic alcohols are smoothly converted with CO2 into a unique class of unexplored cyclic alkylidene carbonates. These systems, for the first time, also achieve the direct carboxylative cyclization of primary propargylic alcohols. The silver-DavePhos catalyst is further applied for the bis-carboxylative cyclization of primary propargyl derivatives, thereby providing an effective route to a series of previously inaccessible and industrially relevant α-alkylidene cyclic carbonates.

A copper-CF2 H complex generated in situ from copper thiocyanate and TMSCF2 H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups-a largely unexplored substituent with highly promising properties-into drug-like molecules.

Practical one-pot procedures were developed for both Sandmeyer-type trifluoromethylations and trifluoromethylthiolations. Starting from broadly available (hetero)aromatic amines, various benzotrifluorides were synthesized in high yields via in situ diazotization and copper-mediated trifluoromethylation using the inexpensive Ruppert-Prakash trifluoromethylating reagent. In the presence of sodium thiocyanate as a sulfur source, aryl trifluoromethyl thioethers are exclusively formed.