The Pd(II)-catalyzed and the thermal Claisen rearrangement of 2-alkoxycarbonyl-substituted allyl vinyl ethers

Authors
Hiersemann, M
Citation
M. Hiersemann, The Pd(II)-catalyzed and the thermal Claisen rearrangement of 2-alkoxycarbonyl-substituted allyl vinyl ethers, SYNLETT, (11), 1999, pp. 1823-1825
Citations number
17
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
SYNLETT
ISSN journal
09365214 → ACNP
Issue
11
Year of publication
1999
Pages
1823 - 1825
Database
ISI
SICI code
0936-5214(199911):11<1823:TPATTC>2.0.ZU;2-3
Abstract
Heating the 2-alkoxycarbonyl-substituted allyl vinyl ethers 2a-c as a mixtu re of enol ether double bond isomers in the presence of 5 mol% Pd2Cl2(PhCN) (2) afforded the beta,gamma-alkyl-substituted a-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 re arrangement via a chairlike transition state.