Synthesis of Trifluoromethylthio Compounds from Sulfur‐Containing Precursors

Abstract The trifluoromethylthio group (−SCF 3 ) exhibits several distinctive physicochemical properties and can alter the molecular lipophilicity and other pharmacokinetic properties of functional molecules. Moreover, its potent electron‐withdrawing capability confers enhanced metabolic stability to functional molecules. Molecules containing trifluoromethylthio groups are extensively applied in the synthesis of pharmaceuticals or agrochemicals and have garnered significant attention in recent years. The synthetic routes to trifluoromethylthio groups primarily fall into two categories: direct introduction of −SCF 3 into target molecules, and indirect construction of −SCF 3 through the introduction of −CF 3 into sulfur‐containing precursors. In this review, we delineate approaches developed over the past seven years for the indirect construction of −SCF 3 groups via electrophilic, nucleophilic, radical, or other types of reactions involving −CF 3 groups and sulfur‐containing precursors. These reactions are classified into seven categories depending on the employed: thiols, disulfides, thiosulfates, sodium sulfinates, sulfonyl chlorides, sulfoxides, and other sulfur‐containing precursors.