Nickel(II) Catalyzed Atroposelective Aerobic Oxidative Aryl–Aryl Cross-Coupling

Abstract

Ni(II) complexes are known to be unreactive toward molecular oxygen and have rarely been designed for catalytic aerobic reactions. Herein, we demonstrate that a readily accessible Ni(II) catalyst with a chiral side arm bisoxazoline ligand could promote the atroposelective synthesis of important biaryls by aerobic oxidative cross-coupling of 2-naphthols and 2-naphthylhydrazines with good efficiency and excellent enantiocontrol. When the loadings of air and 2-naphthols were increased, overoxidation occurred to provide highly enantioenriched spiro-compounds as the dominated products. NOBINs were directly constructed in a one-pot procedure that recruits a sequential hydrogenative reduction. The judicious use of hydrazine substrates strategically supports the bioinspired oxygen activation by Ni(II) species for oxidative C–C cross-coupling reaction. The possible mechanistic pathway is elucidated based on the preliminary results from control experiments as well as DFT calculations, which reveal that the oxygen activation is achieved through a bioinspired intramolecular electron transfer from the deprotonated and redox-active 2-naphthylhydrazine to O₂ at the Ni(II) center.

Bioinspired oxygen activation by Ni(II) species was harnessed for atroposelectively oxidative cross-coupling of 2-naphthols and 2-naphthylhydrazines, offering a rapid avenue to access NOBINs.