Enantioselective Construction of Spirocyclohexenones via Ni-Catalyzed Double Arylative Cyclization of Alkyne-Tethered Malononitriles.

We report a nickel-catalyzed double arylative cyclization of bis(alkyne)-tethered malononitriles with aryl boronic acids, delivering spirocyclohexenones in moderate yields and high enantioselectivities (up to 97:3 er). The method exhibits a broad substrate scope, is amenable to gram-scale synthesis, and enables downstream transformations through stereocontrolled 1,2-reduction of the ketones to diols. A complementary reductive arylative cyclization employing aryl iodides was also developed. This strategy provides a direct route to enantioenriched spirocycles from simple precursors, offering concise access to complex stereochemical architectures.