Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

Abstract The increasing demand of organofluorine compounds in medicine, agriculture, and materials sciences makes sophisticated methods for their synthesis ever more necessary. Nowadays, not only the C−F bond formation but also the selective C−F bond cleavage of readily available poly‐ or perfluorine‐containing compounds have become powerful tools for the effective synthesis of organofluorine compounds. The defluorinative cross‐coupling of trifluoromethyl alkenes with various nucleophiles or radical precursors in an S N 2’ manner is a convergent route to access gem ‐difluoroalkenes, which in turn react with nucleophiles or radical precursors via an S N V‐type reaction. If the S N V reactions occur intramolecularly, the dual C−F bond cleavage of trifluoromethyl alkenes allows facile assembly of monofluorinated cyclic skeletons with structural complexity and diversity. In this personal account, we summarized the advances in this field on the basis of coupling and cyclization partners, including binucleophiles, alkynes, diradical precursors and radical precursors bearing a nucleophilic site. Accordingly, the annulation reactions can be achieved by base‐mediated sequential S N 2′/S N V reactions, transition metal catalyzed or mediated reactions, photoredox catalysis, and the combination of photocatalytic reactions with S N V reaction. In the context of seminal works of others in this field, a concise summary of the contributions of the authors is also offered.