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

Ziyong Wang , Walid Lamine , Karinne Miqueu (1) , Shih-Yuan Liu (2)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
2 BC - Boston College

We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3enynes utilizing DFT calculations, 31 P NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis. Our mechanistic study provides evidence against the conventional inner-sphere b-migratory insertion mechanism. Instead, a syn outer-sphere oxidative addition mechanism featuring a Pd-p-allyl intermediate followed by coordination-assisted rearrangements is consistent with all the experimental observations.

Domaines: Chimie; Chimie théorique et/ou physique

Ziyong Wang, Walid Lamine, Karinne Miqueu, Shih-Yuan Liu. A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes. Chemical Science, 2023, 14 (8), pp.2082 - 2090. ⟨10.1039/d2sc05828f⟩. ⟨hal-04007526⟩