Nickel‐Catalyzed cine ‐Substitution Toward Carbonyl Dance

ABSTRACT 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 K 3 PO 4 , 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.