Mechanism and Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed Suzuki–Miyaura Coupling with Benzylic Esters: A Computational Study

Nickel catalysts have shown unique ligand control of stereoselectivity in the Suzuki–Miyaura cross-coupling of boronates with benzylic pivalates and derivatives involving C(sp3)–O cleavage. The SIMes ligand (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) produces the stereochemically inverted C–C coupling product, while the tricyclohexylphosphine (PCy3) ligand delivers the retained stereochemistry. We have explored the mechanism and origins of the...