2 research outputs found

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

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    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

    C−C, C−O, C−N Bond Formation on sp 2

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