Off-Cycle Processes in Pd-Catalyzed Cross-Coupling of Carboranes.

ABSTRACT: Off-cycle processes in catalytic reactions can dramatically influence the outcome of the chemical transformation and affect its yield, selectivity, rate, and product distribution. While the generation of off-cycle intermediates can complicate reaction coordinate analyses or hamper catalytic efficiency, the generation of such species may also open new routes to unique chemical products. Recently, we reported the Pd-mediated functionalization of carboranes with a range of O-, N-, and C-based nucleophiles. By utilizing a Pd-based catalytic system supported by a biaryl phosphine ligand developed by Buchwald and co-workers, we discovered an off-cycle isomerization process ("cage-walking") that generates four regioisomeric products from a single halogenated boron cluster isomer. Here we describe

SUBMITTER: Dziedzic RM 

PROVIDER: S-EPMC7996392 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature