Theoretical Clarification of Overall Mechanism in the Cross-Coupling Reaction between Conjugated Diene and Heterocyclic Compound by Ru(0) Catalyst

Abstract

Mechanistic studies for linear cross-dimerization between 2,3-dimethylbuta-1,3-diene and 2,5-dihydrofuran by a Ru(0) complex, Ru(η⁶-naphthalene) (η⁴–1,5-COD), were performed computationally. The rate-determining steps of main and side reactions are different mechanisms, and correspond to the reductive elimination step and the oxidative coupling step, respectively. This suggests that the yield of the main product may be improved by modification of the heterocyclic compound or catalyst structure. In addition, the computational studies predicted that cross-dimerization between 2,3-dimethylbuta-1,3-diene and 2,5-dihydropyrrole may occur via a similar reaction mechanism.