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

Published in: Journal of the American Chemical Society (2017)

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.

Keyphrases

room temperature
iron deficiency
molecular dynamics
density functional theory
molecular dynamics simulations
electron transfer