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Synlett 1999; 1999(11): 1823-1825
DOI: 10.1055/s-1999-2932
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The Pd(II)-Catalyzed and the Thermal Claisen Rearrangement of 2-Alkoxycarbonyl-Substituted Allyl Vinyl Ethers

Martin Hiersemann*
  • *Institut für Organische Chemie der Technischen Universität Dresden, D-01062, Germany; Fax +49 3 51 4 63 70 30; E-mail: martin.hiersemann@chemie.tu-dresden.de
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Publication Date:
31 December 1999 (online)

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Heating the 2-alkoxycarbonyl-substituted allyl vinyl ethers 2a-c as a mixture of enol ether double bond isomers in the presence of 5 mol% Pd2Cl2(PhCN)2 afforded the β,γ-alkyl-substituted α-keto esters 3a-c as an anti:syn >9 : 1 mixture of diastereomers. (E,E)-2a-c rearranges Pd(II)-catalyzed via a boatlike transition state whereas (Z,E)-2a-c undergoes the thermal rearrangement via a chairlike transition state.

rearrangements - palladium - catalysis - esters - diastereoselectivity

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