Evidence for in situ catalyst modification during the Pd-catalyzed conversion of aryl triflates to aryl fluorides

J Am Chem Soc. 2011 Nov 16;133(45):18106-9. doi: 10.1021/ja208461k. Epub 2011 Oct 21.

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Catalysis
  • Hydrocarbons, Fluorinated / chemical synthesis*
  • Hydrocarbons, Fluorinated / chemistry
  • Mesylates / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Palladium / chemistry*
  • Stereoisomerism

Substances

  • Hydrocarbons, Fluorinated
  • Mesylates
  • Organometallic Compounds
  • Palladium
  • trifluoromethanesulfonic acid