Recent Advances in C–H Perfluoroalkyl Thiolation and Perfluoroalkyl Sulfonylation

This review comprehensively summarizes the recent advances in the direct C–H perfluoroalkyl thiolation and perfluoroalkyl sulfonylation, focusing on the incorporation of −SCF3 and −SO2CF3 motifs. Due to their exceptional lipophilicity, electron-withdrawing nature, and metabolic stability, these fluorine-containing groups are highly valuable in pharmaceutical, agrochemical, and material sciences. The contents of this review are systematically organized according to the hybridization of the central carbon atom (sp, sp2, sp3) and cover both transition-metal-catalyzed and transition metal-free methodologies. Key developments in electrophilic trifluoromethylthiolating reagents, such as hypervalent iodine compounds, N-trifluoromethylthiosaccharin, and related derivatives, are highlighted. The mechanism, scope, limitation, and application of typical reactions are discussed, emphasizing strategies to overcome challenges in regioselectivity and functional group compatibility. The review also explores emerging trends in photocatalytic, electrochemical, and dual catalytic systems, underscoring the move toward more sustainable and efficient synthetic routes. Finally, future perspectives and potential applications in the synthesis of bioactive molecules and functional materials are discussed.