Nickel-catalyzed skeletal transformation of tropone derivatives via C–C bond activation: catalyst-controlled access to diverse ring systems

Abstract

We report herein on nickel-catalyzed carbon–carbon bond cleavage reactions of 2,4,6-cycloheptatrien-1-one (tropone) derivatives. When a Ni/N-heterocyclic carbene catalyst is used, decarbonylation proceeds with the formation of a benzene ring, while the use of bidentate ligands in conjunction with an alcohol additive results in a two-carbon ring contraction with the generation of cyclopentadiene derivatives. The latter reaction involves a nickel–ketene complex as an intermediate, which was characterized by X-ray crystallography. The choice of an appropriate ligand allows for selective synthesis of four different products via the cleavage of a seven-membered carbocyclic skeleton. Reaction mechanisms and ligand-controlled selectivity for both types of ring contraction reactions were also investigated computationally.