Defluorinative Functionalization of Pd(II) Fluoroalkyl Complexes
Michael M. Wade Wolfe, James P. Shanahan, Jeff W. Kampf, Nathaniel K. Szymczak
Abstract
When subjected to arylboranes, anionic trifluoromethyl and difluorobenzyl palladium(II) complexes undergo fluoride abstraction followed by 1,1-migratory insertion. The resulting intermediate fluoroalkyl species can be induced to undergo a subsequent transmetalation and reductive elimination from either an in situ formed fluoroboronate (FB(Ar3)−) or an exogenous boronic acid/ester (ArB(OR)2) and nucleophilic activator, representing a net defluorinative arylation reaction. The latter method enabled a structurally diverse substrate scope to be prepared from either an isolated palladium-CF3 complex, or from Pd(PPh3)4 and other commercially available reagents.
Topics & Concepts
ChemistryTransmetalationPalladiumReagentBoronic acidTrifluoromethylNucleophileSurface modificationCombinatorial chemistryFluorideSubstrate (aquarium)FluorineOrganic chemistryCatalysisInorganic chemistryOceanographyPhysical chemistryGeologyAlkylFluorine in Organic ChemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods