Wong KC1,2, Ng E1, Wong WT1,3, Chiu P4.
Chemistry. 2016 Mar 7;22(11):3709-12. doi: 10.1002/chem.201504870. Epub 2016 Feb 4.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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.