title: Catalytic asymmetric Claisen rearrangement of Gosteli-type allyl vinyl ethers: total synthesis of (-)-9,10-dihydroecklonialactone B.
abstract: The enantioselective synthesis of (-)-9,10-dihydroecklonialactone B is described. The catalytic asymmetric Claisen rearrangement of a Gosteli-type allyl vinyl ether was utilized to afford an acyclic α-keto ester building block endowed with functionality amenable to the preparation of the carbocyclic target molecule by suitable postrearrangement transformations: A highly diastereoselective Corey-Bakshi-Shibata reduction of a β-chiral α-keto ester and a reductive homologation of an α-hydroxy ester. A transprotection tactic by a chemoselective intramolecular 6-exo-trig iodoetherification enabled regioselective ring-closing alkene metatheses to afford the 5- as well as the 14-membered ring, however, with mixed success in terms of E/Z selectivity.
authors.affiliation: Fakultät Chemie und Chemische Biologie, Technische Universität Dortmund , 44227 Dortmund, Germany.
authors.forename: Julia
authors.initials: J
authors.lastname: Becker
authors.forename: Lena
authors.initials: L
authors.lastname: Butt
authors.forename: Valeska
authors.initials: V
authors.lastname: von Kiedrowski
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Mischler
authors.forename: Florian
authors.initials: F
authors.lastname: Quentin
authors.forename: Martin
authors.initials: M
authors.lastname: Hiersemann