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Sulfur-Directed Olefin Oxidations: Observation of Divergent Reaction Mechanisms in the Palladium-Mediated Acetoxylation of Unsaturated Thioacetals

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. Green open access

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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 > 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: http://discovery.ucl.ac.uk/id/eprint/1304463
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