Intramolecular One-Carbon Homologation of Unstrained Ketones via C–C Activation-Enabled 1,1-Insertion of Alkenes

Here, we describe the development of a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a distinct approach to access various substituted 1-indanones. Computational mechanistic studies reveal that the formal 1,1-insertion is realized by a selective C(sp²)-C(sp³) activation and turnover limiting 2,1-insertion into the alkene, followed by a facile β-H elimination and reinsertion process.