Nickel-Catalyzed Enantioselective Arylative Cyclization of Alkyne-Oxime Ethers: Access to Chiral Hydroxylamine Ethers

Chiral hydroxylamines serve as essential scaffolds in modern organic synthesis and are of significant interest in drug discovery. Although asymmetric hydrogenation of oximes is well-established, the development of metal-catalyzed asymmetric oxime ethers addition reactions, especially those employing earth-abundant metal catalysts, has remained limited. Herein, we report the first nickel-catalyzed asymmetric addition of oxime ethers, providing chiral hydroxylamine ethers in moderate to excellent yields (up to 94%) with generally excellent enantioselectivities (up to 99% ee). Moreover, this method enables the construction of chiral hydroxylamine ethers bearing multiple contiguous stereocenters via a substrate-controlled diastereoselective process.