A Systematic DFT Investigation of the Reaction Mechanism and Stereoselectivities in Iron‐Catalyzed Reductive Diene Cyclization

ABSTRACT

The reductive olefin‐coupling strategy enables the coupling of unactivated olefins with electron‐deficient olefins under both intra‐ and intermolecular conditions, providing efficient access to highly substituted and structurally complex polycyclic frameworks. Herein, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism of the Fe(acac) ₃ ‐catalyzed radical cyclization of a model substrate of (6‐methylenecyclohexyl)ethylcyclohex‐1‐ene, and a complete potential energy surface was constructed. Furthermore, the substituent effects on stereoselectivity were systematically investigated. This study provides deeper mechanistic insights into the experimentally observed stereochemical outcomes and offers valuable guidance for the rational design of related transformations toward the synthesis of polycyclic molecules.