Mechanistic Insights into the Pd-Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer-sphere Mechanism Involving a Palladium Hydride Intermediate
2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 6, 1520-1524 p.Article in journal (Refereed) Published
The mechanism of direct amination of allyl alcohol by a palladium triphenylphosphite complex has been explored. Labelling studies show that the reaction proceeds through a π-allylpalladium intermediate. A second-order dependence of reaction rate on allyl alcohol concentration was observed. Kinetic isotope effect studies and ESI-MS studies are in agreement with a reaction proceeding through a palladium hydride intermediate in which both O-H bond and C-O bond cleavages are involved in rate-determining steps. A stereochemical study supports an outer-sphere nucleophilic attack of the π-allylpalladium intermediate giving complete chiral transfer from starting material to product.
Place, publisher, year, edition, pages
2014. Vol. 20, no 6, 1520-1524 p.
Analytical Chemistry Physical Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-215613DOI: 10.1002/chem.201303431ISI: 000337300000008PubMedID: 24403056OAI: oai:DiVA.org:uu-215613DiVA: diva2:687799