TY - JOUR T1 - A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes. AU - Wang,Ziyong, AU - Lamine,Walid, AU - Miqueu,Karinne, AU - Liu,Shih-Yuan, Y1 - 2023/01/17/ PY - 2022/10/21/received PY - 2023/1/4/accepted PY - 2023/2/27/entrez PY - 2023/2/28/pubmed PY - 2023/2/28/medline SP - 2082 EP - 2090 JF - Chemical science JO - Chem Sci VL - 14 IS - 8 N2 - We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes utilizing DFT calculations, 31P 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 syn outer-sphere oxidative addition mechanism featuring a Pd-π-allyl intermediate followed by coordination-assisted rearrangements is consistent with all the experimental observations. SN - 2041-6520 UR - https://www.unboundmedicine.com/medline/citation/36845936/A_syn_outer_sphere_oxidative_addition:_the_reaction_mechanism_in_Pd/Senphos_catalyzed_carboboration_of_13_enynes_ DB - PRIME DP - Unbound Medicine ER -