Catalyst Modification during the Pd-Catalyzed Conversion of Aryl Triflates to Aryl Fluorides

T. J. Maimone, Milner, P. J. , Kinzel, T. , Zhang, Y. , Takase, M. K. , and Buchwald, S. L. “Evidence for in situ Catalyst Modification during the Pd-Catalyzed Conversion of Aryl Triflates to Aryl Fluorides”, J. Am. Chem. Soc., 2011, 133(45), 18106-18109.

Abstract:

A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C–F reductive elimination from a LPdII(aryl)F complex (L = t-BuBrettPhos or RockPhos) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in situ, serves as the actual supporting ligand during catalysis with such substrates. A preliminary study of the reactivity of a LPdII(aryl)F complex based on this modified ligand is reported.

Authors

Thomas Maimone, Phillip J. Milner, Tom Kinzel, Yong Zhang