Mechanistic Insights into the Pd‐Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer‐Sphere Mechanism Involving a Palladium Hydride Intermediate. Issue 6 (8th January 2014)

• Record Type: Journal Article
• Authors: Sawadjoon, Supaporn; Sjöberg, Per J. R.; Orthaber, Andreas; Matsson, Olle; Samec, Joseph S. M.
• Is Part Of: Chemistry. Volume 20:Issue 6(2014)
• Page Start: 1520
• Page End: 1524
• Publication Date: 2014-01-08
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201303431
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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.</p> </abstract>