Transition-metal-catalyzed asymmetric defluorinative reactions

Organofluorides have found wide applications in materials science, medicinal chemistry, agrochemistry, and organic synthesis. The unique reactivity and properties of fluorine-containing compounds render them worth investigating in asymmetric synthesis to access valuable enantioenriched molecules. Although metal catalysis paves the way for the chemoselective and regioselective defluorination of fluorine-containing molecules, the functionalization of the elusive C-F bond integrated into catalytic enantioselective transformation remains highly sought after. In this review, the latest achievements in transition-metal-catalyzed enantioselective defluorinative coupling reactions have been comprehensively summarized on the basis of the classification of transition-metal catalysts. Compared with other heteroatoms, special emphasis is placed on the function of the fluorine atom as a detachable “chemical handle” for the enantioselective transformation of easily accessible fluorine-containing chemicals, such as trifluoromethyl alkenes, allylic fluorides, propargyl gem-difluorides, gem-difluoroalkenes, polyfluoroarenes, dienyl fluorides, and trifluoromethyl (hetero)arenes. We aim to inspire chemists to continue their interest in both research topics of C-F bond activation and asymmetric catalysis.