Mechanistic Insights into the Pd-Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer-sphere Mechanism Involving a Palladium Hydride Intermediate

Mechanistic Insights into the Pd-Catalyzed Direct Amination of Allyl Alcohols : Evidence for an Outer-sphere Mechanism Involving a Palladium Hydride Intermediate

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.

Sjöberg, Per J RUppsala universitet,Analytisk kemi(Swepub:uu)psj18455 (författare)
Orthaber, AndreasUppsala universitet,Molekylär biomimetik(Swepub:uu)ortan368 (författare)
Matsson, OlleUppsala universitet,Fysikalisk-organisk kemi(Swepub:uu)oma05252 (författare)
Samec, Joseph S MUppsala universitet,Syntetisk organisk kemi(Swepub:uu)jossa512 (författare)
Uppsala universitetSyntetisk organisk kemi (creator_code:org_t)

Ingår i:Chemistry - A European Journal: Wiley20:6, s. 1520-15240947-65391521-3765

Av författaren/redakt...: Sawadjoon, Supap ...; Sjöberg, Per J R; Orthaber, Andrea ...; Matsson, Olle; Samec, Joseph S ...

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