1590438-52-0Relevant academic research and scientific papers
Mechanistic insights into the Pd-catalyzed direct amination of allyl alcohols: Evidence for an outer-sphere mechanism involving a palladium hydride intermediate
Sawadjoon, Supaporn,Sjoeberg, Per J. R.,Orthaber, Andreas,Matsson, Olle,Samec, Joseph S. M.
, p. 1520 - 1524 (2014)
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. Two cleavages: The mechanism of the direct amination of allyl alcohol by palladium complexes bearing triphenylphosphite ligands has been explored. Kinetic isotope and ESI-MS studies are in good agreement with that both Oi￡H bond and Ci￡O bond cleavages are involved in rate-determining steps. Furthermore, stereochemical studies support an outer-sphere nucleophilic attack of the π-allylpalladium intermediate. Copyright
