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A Syn Outer-Sphere Oxidative Addition: The Reaction Mechanism in Pd/Senphos-Catalyzed Carboboration of 1,3-Enynes

11 October 2022, Version 1
Working Paper
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

Pd Catalysis
Boron
enyne
azaborine
reaction mechanism
computational chemistry
physical organic chemistry
phosphine ligands
C-Boron enolates

Supplementary materials

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Supporting Information
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Experimental procedures, compound characterization data, computational information (PDF)
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Now Published

A Syn Outer-Sphere Oxidative Addition: The Reaction Mechanism in Pd/Senphos-Catalyzed Carboboration of 1,3-Enynes [opens in a new tab]
Ziyong Wang, Walid Lamine, Karinne Miqueu, Shih-Yuan Liu journal article
Chemical Science
Online publication date: 2023

Version History

Oct 11, 2022 Version 1

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The content is available under CC BY NC ND 4.0 [opens in a new tab]

DOI

10.26434/chemrxiv-2022-g3qng
D O I: 10.26434/chemrxiv-2022-g3qng [opens in a new tab]

Funding

National Institutes of Health
R01GM136920
National Institutes of Health
1S10OD026910-01A1
National Science Foundation
CHE-2117246
University of Pau CINES/GENCI
A011080045

Author’s competing interest statement

The author(s) have declared they have no conflict of interest with regard to this content

Ethics

The author(s) have declared ethics committee/IRB approval is not relevant to this content

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