Mechanism of Nakamura’s Bisphosphine-Iron-Catalyzed Asymmetric C(sp2)–C(sp3) Cross-Coupling Reaction: The Role of Spin in Controlling Arylation Pathways

Quantum mechanical calculations are employed to investigate the mechanism and origin of stereoinduction in asymmetric iron-catalyzed C(sp2)–C(sp3) cross-coupling reaction between Grignard reagents and α-chloroesters. A coherent mechanistic picture of this transformation is revealed. These results have broad implications for understanding the mechanisms of iron-catalyzed cross-coupling reactions and rational design of novel iron-based catalysts for asymmetric transformations.