title: Mechanistic insights into the Pd-catalyzed direct amination of allyl alcohols: evidence for an outer-sphere mechanism involving a palladium hydride intermediate.
abstract: 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.
authors.affiliation: Department of Chemistry, BMC, Uppsala University, Box 576, 751 23 Uppsala (Sweden), Fax: (+46) 18-4714988.
authors.forename: Supaporn
authors.initials: S
authors.lastname: Sawadjoon
authors.forename: Per J R
authors.initials: PJ
authors.lastname: Sjöberg
authors.forename: Andreas
authors.initials: A
authors.lastname: Orthaber
authors.forename: Olle
authors.initials: O
authors.lastname: Matsson
authors.forename: Joseph S M
authors.initials: JS
authors.lastname: Samec
keywords: alcohols; allylation; kinetics; palladium; reaction mechanisms