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The Regio- and Stereospecific Intermolecular Dehydrative Alkoxylation of Allylic Alcohols Catalyzed by a Gold(I) N-Heterocyclic Carbene Complex

Authors

  • Dr. Paramita Mukherjee,

    1. Department of Chemistry, Duke University, French Family Science Center, Durham, NC 27708 (USA), Fax: (+1) 919-660-1605
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  • Prof. Ross A. Widenhoefer

    Corresponding author
    1. Department of Chemistry, Duke University, French Family Science Center, Durham, NC 27708 (USA), Fax: (+1) 919-660-1605
    • Department of Chemistry, Duke University, French Family Science Center, Durham, NC 27708 (USA), Fax: (+1) 919-660-1605

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Abstract

A 1:1 mixture of [AuCl(IPr)] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) and AgClO4 catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to form allylic ethers. These transformations are regio- and stereospecific with preferential addition of the alcohol nucleophile at the γ-position of the allylic alcohol syn to the departing hydroxyl group and with predominant formation of the E stereoisomer. The minor α regioisomer is formed predominantly through a secondary reaction manifold involving regioselective γ-alkoxylation of the initially formed allylic ether rather than by the direct α-alkoxylation of the allylic alcohol.

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