title: Oxyanionic sigmatropic rearrangements relevant to cyclooctadienone formation in penostatins I and F.
abstract: The results of several experiments designed to probe the energetic viability of a reaction path for generation of penostatins I (3) and F (4) via spontaneous [3,3]-sigmatropic rearrangement are reported. In particular, the enolate derived from the 2-vinyl-6-acyldihydropyran 8-cis gave cyclooctadienone 12 via facile anionic oxy-Claisen rearrangement, demonstrating the feasibility of such an event.
authors.affiliation: Department of Chemistry, University of Minnesota, 207 Pleasant Street SE Minneapolis, Minnesota 55455, USA.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Jansma
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Hoye
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D010407:Penicillium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; C496162:penostatin F; C576865:penostatin I