Nucleophilic Addition versus Migratory Insertion Pathways in the Gold-Catalyzed Heck Reaction: A Computational Study.

ABSTRACT: The initial reaction steps in the formation of Heck-type arylated alkenes catalyzed by P^N chelated Au(III) complexes have been studied computationally. Two mechanistic alternatives have been explored: (1) alkene coordination and insertion into a gold-carbon bond, and (2) nucleophilic attack on a gold(III) alkene adduct. The common starting point, the [(P^N)AuPh(alkene)]²⁺ dication (alkene = C₂H₄, H₂C═CHEt, or H₂C═CEt₂), shows unequal bonding to the olefinic carbons of the 1-alkenes (P^N = 1,2-C₆H₄NMe₂(PR₂); R = H, Me, 1-adamantyl). This polarization increases with steric hindrance and with the inclusion of an OTf^- anion in the model. While the reaction pathways are stro

SUBMITTER: Budzelaar PHM 

PROVIDER: S-EPMC12284628 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature