Aryl-CF(3) bond-forming reductive elimination from palladium(IV).
This communication describes oxidatively induced Ar-CF(3) bond-forming reductive elimination from new Pd(II) complexes of general structure (L approximately L)Pd(II)(Ar)(CF(3)). The electrophilic fluorinating reagent N-fluoro-2,4,6-trimethylpyridinium triflate promotes these reactions in good to excellent yields. The palladium(IV) intermediate ((t)Bu-bpy)Pd(IV)(CF(3))(F)(OTf)(C(6)H(4)F) has been isolated, characterized, and demonstrated to undergo high yielding Ar-CF(3) coupling upon thermolysis. This work provides an attractive conceptual framework for the development of Pd(II/IV)-catalyzed arene trifluoromethylation reactions.
Ball
Nicholas D
ND
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, USA.
Kampf
Jeff W
JW
Sanford
Melanie S
MS
D001665:Binding Sites; D018360:Crystallography, X-Ray; D005609:Free Radicals / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*
D005609:Free Radicals; D006845:Hydrocarbons, Fluorinated; D008024:Ligands; D009942:Organometallic Compounds; D010165:Palladium