Nickel-Catalyzed cine-Substitution Toward Carbonyl Dance

Catalytic transformations that enable the positional exchange of functional groups provide powerful tools for the structural diversification of organic molecules. Herein, we report a nickel-catalyzed cine-substitution that achieves 1,2-carbonyl translocation (carbonyl dance) from tetralone derivatives. Under the optimized conditions using Ni(dcype)(CO)₂ and K₃PO₄, a variety of amines underwent selective cine-substitution to afford the corresponding enamines, which could be readily hydrolyzed to give β-tetralones bearing translocated carbonyl groups. This reaction proceeds in high yields with excellent regioselectivity and tolerates various heteroatom nucleophiles, including secondary anilines, phenoxazine, and a sterically hindered alcohol. Moreover, a one-pot protocol starting from tetralone was established, enabling sequential pivalate formation, cine-substitution, and hydrolysis or oxidation to provide either the β-tetralone or tertiary amine with a naphthyl substituent, although a solvent-removal step is required during the sequence. This study demonstrates a new catalytic platform for functional group transposition, expanding the scope of carbonyl migration chemistry via nickel-catalyzed cine-substitution.