Regiodivergent C-H and Decarboxylative C-C Alkylation by Ruthenium Catalysis:orthoversusmetaPosition-Selectivity

Ruthenium(II)biscarboxylate complexes enabled the selective alkylation of C-H and C-C bonds at theortho- ormeta-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 ofortho-/meta-selectivities. Detailed mechanistic studies by experiment and computation were performed and provided strong support for an oxidative addition/reductive elimination process forortho-alkylations, while a homolytic C-X cleavage was operative for themeta-selective transformations.