A reaction of acetonitrile-solvated AgOCF3 with 1 equiv. of Aryl-BIAN ligand in THF at room-temperature afforded the silver(i) complex (Aryl-BIAN)AgOCF3 (1) in 75% yield. The crystal structure of this silver(i) trifluoromethoxide was determined by single-crystal X-ray crystallography. The molecular structure of 1 shows the metal centre bound to one molecule of BIAN, one trifluoromethoxide and one THF solvate, resulting in a distorted tetrahedral silver. Density functional theory (DFT) calculations and the natural bond orbital (NBO) analysis were conducted to give insights into the electronic structure of 1 and the bonding characters of the OCF3 group. The reactivity of 1 towards trifluoromethoxylation of organic halides was also examined; a reaction with benzyl bromides gave the desired products of benzyl trifluoromethyl ethers in good to excellent yields.

Herein, a copper-catalyzed 2,2,2-trifluoroethylthiolation reaction of aryl bromides and iodides with elemental sulfur, and 1,1,1-trifluoro-2-iodoethane is described. The reaction showed excellent functional group tolerance and allowed the synthesis of various substituted aryl 2,2,2-trifluoroethyl thioethers with good to excellent yields. This transformation constitutes a one-pot synthesis of 2,2,2-trifluoroethylthiolated compounds from inexpensive, readily available starting materials. Utility of the protocol was further demonstrated in the late-stage synthesis of the pirfenidone derivative. The copper thiolate species were prepared and proposed as key intermediates in the catalytic cycle.

2-Trifluoromethylated furans and dihydrofuranols were tunably synthesized from the cyclization of β-ketonitriles with 3-bromo-1,1,1-trifluoroacetone mediated by bases. In addition, dehydration of dihydrofuranol compounds with concentrated sulfuric acid gave another 2-(trifluoromethyl)­furans isomer. The developed methodology exhibits an excellent functional group tolerance for both aromatic and aliphatic β-ketonitriles.

A copper-mediated difluoromethylenation of o-bromophenols with trifluoromethanethiolate is described. This one-pot protocol proceeds through an intermolecular addition of S=CF (resulting from the decomposition of trifluoromethanethiolate) to o-bromophenols followed by intramolecular C-S coupling to form 2,2-difluoro-1,3-benzoxathioles. This method is compatible with a broad range of substrates and enables the late-stage difluoromethylenation of several functionally dense druglike o-bromophenols.

A copper-catalyzed synthesis of trifluoromethylated bis(indolyl)arylmethanes via reaction of 2-arylindoles with 2,2,2-trifluoroacetohydrazide was developed.