title: Evidence for in situ catalyst modification during the Pd-catalyzed conversion of aryl triflates to aryl fluorides.
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 LPd(II)(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 LPd(II)(aryl)F complex based on this modified ligand is reported.
authors: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
authors: Thomas J
authors: TJ
authors: Maimone
authors: Phillip J
authors: PJ
authors: Milner
authors: Tom
authors: T
authors: Kinzel
authors: Yong
authors: Y
authors: Zhang
authors: Michael K
authors: MK
authors: Takase
authors: Stephen L
authors: SL
authors: Buchwald
mesh_terms: D002384:Catalysis; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry; D008698:Mesylates / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D006845:Hydrocarbons, Fluorinated; D008698:Mesylates; D009942:Organometallic Compounds; D010165:Palladium; C012077:trifluoromethanesulfonic acid