Mann, SE;
Aliev, AE;
Tizzard, GJ;
Sheppard, TD;
(2011)
Sulfur-Directed Olefin Oxidations: Observation of Divergent Reaction Mechanisms in the Palladium-Mediated Acetoxylation of Unsaturated Thioacetals.
Organometallics
, 30
(7)
1772 - 1775.
10.1021/om2000585.
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Abstract
The Pd-mediated oxidation of unsaturated thioacetals gives either allyl or vinyl esters, depending on the substrate structure. We report the characterization of a range of sulfur-stabilized palladium intermediates via a combined computational and experimental NMR approach, demonstrating that the oxidation proceeds via two divergent reaction mechanisms. We were also able to synthesize an unusual sigma-bound Pd complex, via acetoxypalladation of an unsaturated dithiane, which was characterized by X-ray crystallography.
| Type: | Article |
|---|---|
| Title: | Sulfur-Directed Olefin Oxidations: Observation of Divergent Reaction Mechanisms in the Palladium-Mediated Acetoxylation of Unsaturated Thioacetals |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/om2000585 |
| Publisher version: | http://dx.doi.org/10.1021/om2000585 |
| Language: | English |
| Additional information: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/om2000585. |
| Keywords: | catalyzed allylic acetoxylation, sigma-organopalladium complexes, C-H oxidation, terminal olefins, alkenes, acids, functionalization, acetates, insights, oxidant |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1304463 |
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