Regiodivergent C−H and Decarboxylative C−C Alkylation by Ruthenium Catalysis: <i>ortho</i> versus <i>meta</i> Position‐Selectivity

Abstract

Ruthenium(II)biscarboxylate complexes enabled the selective alkylation of C-H and C-C bonds at the ortho- or meta-position. ortho-C-H Alkylations were achieved with 4-, 5- as well as 6-membered halocycloalkanes. Furthermore, the judicious choice of the directing group allowed for a full control of ortho-/meta-selectivities. Detailed mechanistic studies by experiment and computation were performed and provided strong support for an oxidative addition/reductive elimination process for ortho-alkylations, while a homolytic C-X cleavage was operative for the meta-selective transformations.