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, P NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis. Our mechanistic study provides evidence against the conventional inner-sphere β-migrat...

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Bibliographic Details
Published in:	Chemical science (Cambridge) Vol. 14; no. 8; pp. 2082 - 2090
Main Authors:	Wang, Ziyong, Lamine, Walid, Miqueu, Karinne, Liu, Shih-Yuan
Format:	Journal Article
Language:	English
Published:	England Royal Society of Chemistry 22-02-2023 The Royal Society of Chemistry
Subjects:	Chemical Sciences Chemistry NMR Nuclear magnetic resonance or physical chemistry Reaction mechanisms Theoretical and
Online Access:	Get full text
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Summary:	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.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	2041-6520 2041-6539
DOI:	10.1039/d2sc05828f