A 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-mig...
Saved in:
| Published in: | Chemical science (Cambridge) Vol. 14; no. 8; pp. 282 - 29 |
|---|---|
| Main Authors: | , , , |
| Format: | Journal Article |
| Published: |
22-02-2023
|
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | 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.
A combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes reveals a
syn
outer-sphere oxidative addition mechanism featuring a Pd-π-allyl intermediate followed by coordination-assisted rearrangements. |
|---|---|
| Bibliography: | Electronic supplementary information (ESI) available: Experimental and computational details, synthetic procedures, analytical data, NMR spectra and kinetic studies (PDF). Optimized Cartesian coordinates XYZ See DOI https://doi.org/10.1039/d2sc05828f |
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/d2sc05828f |