title: Copper Hydride Catalyzed Reductive Claisen Rearrangements.
abstract: An efficient reductive Claisen rearrangement, catalyzed by in situ generated copper hydride and stoichiometric in diethoxymethylsilane, has been developed. Yields of up to 95 % with good to excellent diastereoselectivities were observed in this reaction. Mechanistic studies showed that the stereospecific rearrangement proceeded via a chair transition state of (E)-silyl ketene acetals as intermediates and not via the copper enolates.
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.|Department of Pharmacology and Pharmacy, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
authors.forename: Kong Ching
authors.initials: KC
authors.lastname: Wong
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
authors.forename: Elvis
authors.initials: E
authors.lastname: Ng
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.|Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnical University, Hung Hom, Hong Kong, P. R. China.
authors.forename: Wing-Tak
authors.initials: WT
authors.lastname: Wong
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China. pchiu@hku.hk.
authors.forename: Pauline
authors.identifier: http://orcid.org/0000-0001-5081-4756
authors.initials: P
authors.lastname: Chiu
keywords: Claisen rearrangements; copper; hydride; reduction; silanes