Copper-Catalyzed Asymmetric Tertiary Radical Cyanation\nfor the Synthesis of Chiral Tetrasubstituted Monofluoroacyl Nitriles

The\nconstruction of chiral tetrasubstituted α-fluoro-α-cyano\ncarbonyl compounds remains a key challenge in synthetic organic chemistry\nbecause of their popularity in multiple disciplines. In this paper,\nwe report the copper-catalyzed asymmetric fluorinated tertiary radical\ncyanation reaction of cyclic α-iodo-α-fluoroindanones\nwith TMSCN to achieve chiral nitriles with carbon–fluorine\nquaternary stereogenic centers. Thus, an array of optically active\ntetrasubstituted monofluoroacyl nitriles were synthesized with high\nreaction efficiency and excellent enantioselectivities (up to 91%\nyield, 99% ee). Moreover, mechanistic investigations, including experiments,\nwere conducted to clarify the reaction pathway and stereochemical\noutcomes.