A 外层球氧化加成：钯/联萘酚磷催化的 1,3-烯炔碳硼化反应机理

A outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes.

作者信息

Wang Ziyong, Lamine Walid, Miqueu Karinne, Liu Shih-Yuan

机构信息

Department of Chemistry, Boston College Chestnut Hill Massachusetts 02467-3860 USA

Université de Pau et des Pays de l'Adour, E2S UPPA/CNRS, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux IPREM UMR 5254 Hélioparc, 2 Avenue P. Angot 64053 Pau Cedex 09 France

出版信息

Chem Sci. 2023 Jan 17;14(8):2082-2090. doi: 10.1039/d2sc05828f. eCollection 2023 Feb 22.

We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes utilizing DFT calculations, P NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis. Our mechanistic study provides evidence against the conventional inner-sphere β-migratory insertion mechanism. Instead, a outer-sphere oxidative addition mechanism featuring a Pd-π-allyl intermediate followed by coordination-assisted rearrangements is consistent with all the experimental observations.