Palladium‐Catalyzed Desulfinative Cross‐Coupling of Polyhalogenated Aryl Triflates with Aryl Sulfinate Salts: Inversion of Traditional Chemoselectivity†

Comprehensive Summary This paper presents the first general examples of palladium‐catalyzed desulfinative cross‐coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts showing an inversion of the conventional reactivity order of C—Br > C—Cl > C—OTf. The catalyst system, comprising of Pd(OAc)2 and tBuPhSelectPhos, exhibited excellent catalytic reactivity and chemoselectivity toward this reaction. This reaction had a wide range of substrate scopes and provided a simple and efficient method for the construction of functionalized biaryl motifs. Notably, the C—H···Pd interaction from the methine hydrogen of the C2‐cyclohexyl group of the indolyl phosphine ligand with the Pd center may contribute a key factor in reactivity and chemoselectivity. Assisting with density functional theory (DFT) calculations, the results revealed that the oxidative addition step in this reaction was a controlling‐chemoselectivity step.