Pd‐Catalyzed Oxidative C−H Arylation of (Poly)fluoroarenes with Aryl Pinacol Boronates and Experimental and Theoretical Studies of its Reaction Mechanism

We report the synergistic combination of Pd(OAc) 2 and Ag 2 O for the oxidative C−H arylation of (poly)fluoroarenes with aryl pinacol boronates (Ar‐Bpin) in DMF as the solvent. This procedure can be conducted easily in air, and without using additional ligands, to afford the fluorinated unsymmetrical biaryl products in up to 98 % yield. Experimental studies suggest that the formation of [PdL 2 (C 6 F 5 ) 2 ] in DMF as coordinating solvent does not take place under the reaction conditions as it is stable to reductive elimination and thus would deactivate the catalyst. Thus, the intermediate [Pd(DMF) 2 (Ar F )(Ar)] must be formed selectively to give desired arylation products. DFT calculations predict a low barrier (5.87 kcal/mol) for the concerted metalation deprotonation (CMD) process between C 6 F 5 H and the Pd(II) species formed after transmetalation between the Pd(II)X 2 complex and aryl‐Bpin which forms a Pd‐Ar rich species. Thus a Pd(Ar rich )(Ar poor ) complex is generated selectively which undergoes reductive elimination to generate the unsymmetrical biaryl product.