Aryl Fluoride Activation Through Palladium-Magnesium Bimetallic Cooperation: A Mechanistic and Computational Study.

ABSTRACT: Herein is described a mechanistic study of a palladium-catalyzed cross-coupling of aryl Grignard reagents to fluoroarenes that proceeds via a low-energy heterobimetallic oxidative addition pathway. Traditional oxidative additions of aryl chlorides to Pd complexes are known to be orders of magnitude faster than with aryl fluorides, and many palladium catalysts do not activate aryl fluorides at all. The experimental and computational studies outlined herein, however, support the view that at elevated Grignard : ArX ratios (i.e. 2.5 : 1) a Pd-Mg heterobimetallic mechanism predominates, leading to a remarkable decrease in the energy required for Ar-F bond activation. The heterobimetallic transition state for C-X bond cleavage is proposed to involve simultaneous Pd backbonding to the arene and

SUBMITTER: Wu C 

PROVIDER: S-EPMC8248268 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature