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

We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes 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 β-mi...

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Autores principales: Wang, Ziyong, Lamine, Walid, Miqueu, Karinne, Liu, Shih-Yuan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9945512/
https://www.ncbi.nlm.nih.gov/pubmed/36845936
http://dx.doi.org/10.1039/d2sc05828f
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author Wang, Ziyong
Lamine, Walid
Miqueu, Karinne
Liu, Shih-Yuan
author_facet Wang, Ziyong
Lamine, Walid
Miqueu, Karinne
Liu, Shih-Yuan
author_sort Wang, Ziyong
collection PubMed
description We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes 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 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.
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spelling pubmed-99455122023-02-23 A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes Wang, Ziyong Lamine, Walid Miqueu, Karinne Liu, Shih-Yuan Chem Sci Chemistry We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes 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 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. The Royal Society of Chemistry 2023-01-17 /pmc/articles/PMC9945512/ /pubmed/36845936 http://dx.doi.org/10.1039/d2sc05828f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Wang, Ziyong
Lamine, Walid
Miqueu, Karinne
Liu, Shih-Yuan
A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes
title A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes
title_full A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes
title_fullStr A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes
title_full_unstemmed A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes
title_short A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes
title_sort syn outer-sphere oxidative addition: the reaction mechanism in pd/senphos-catalyzed carboboration of 1,3-enynes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9945512/
https://www.ncbi.nlm.nih.gov/pubmed/36845936
http://dx.doi.org/10.1039/d2sc05828f
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