Synthetic and mechanistic studies of Pd-catalyzed C-H arylation with diaryliodonium salts: evidence for a bimetallic high oxidation state Pd intermediate.
This contribution describes the substrate scope and mechanism of Pd-catalyzed ligand-directed C-H arylation with diaryliodonium salts. This transformation was applied to the synthesis of a variety of different biaryl products, using directing groups including pyridines, quinolines, pyrrolidinones, and oxazolidinones. Electronically and sterically diverse aryl groups (Ar) were transferred in high yield using iodine(III) reagents of general structure [Mes-I-Ar]BF(4). Mechanistic investigations have been conducted that establish the kinetic order of the catalytic reaction in each component, determine the resting state of the catalyst and the iodine(III) reagent, quantify the electronic influence of the arylating reagent on the reaction rate, and establish the intra- and intermolecular 1 degree H/D kinetic isotope effect. On the basis of these studies, this transformation is proposed to proceed via turnover-limiting oxidation of the Pd dimer [Pd(N~C)(OAc)](2) (N~C = 3-methyl-2-phenylpyridine) by [Mes-I-Ph]BF(4). This mechanism implicates a bimetallic high oxidation state Pd species as a key catalytic intermediate. The significance of this and other aspects of the proposed mechanism are discussed in detail.
Deprez
Nicholas R
NR
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, USA.
Sanford
Melanie S
MS
D002384:Catalysis; D004583:Electrons; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007477:Ions; D010165:Palladium / Q000737:chemistry*; D012492:Salts
D006841:Hydrocarbons, Aromatic; D007477:Ions; D012492:Salts; D010165:Palladium