New insight into Cu-catalyzed borocarbonylative coupling reactions of alkenes with alkyl halides

• Published in: Journal of catalysis 2023-02, Vol.418, p.263-272
• Main Authors: Liu, Yanhong, Feng, Aili, Zhu, Rongxiu, Liu, Chengbu, Zhang, Dongju
• Format: Article
• Language: English
• Subjects: Alkenes; Alkyl halides; Borocarbonylative; Copper; Density functional theory calculations; IPr and Xantphos ligands
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2023.01.014

DFT calculations show an unexpected mechanism on copper-catalyzed four-component borocarbonylative coupling reaction, and rationalize the experimentally observed regio- and chemoselectivities and substituent effect of alkenes. [Display omitted] •1. A SN2-type C–C coupling mechanism involved CuI-only and two ligands, is provided.•2. The observed regio- and chemoselectivities is rationalized.•3. The substituent effect of alkenes (unactivated vs activated alkenes) is presented. Density functional theory (DFT) calculations were performed to better understand the mechanism of copper-catalyzed four-component borocarbonylative coupling of alkenes with alkyl halides by using bis(pinacolato)diboron as the boron reagent under CO atmosphere as reported in the recent literature. An unexpected reaction mechanism was shown to be viable, which occurs via a CuI-only involved, two-ligand relay-enabled, and no radical-participated copper catalysis with a SN2-type CC coupling fashion. The theoretical results rationalized the experimentally observed regio- and chemoselectivities, and substituent effect of alkenes as well as the fact the reaction is totally inhibited by radical trapping reagents.