title: Synthetic studies on the ingenane diterpenes. An improved entry into a trans-intrabridgehead system.
abstract: [reaction: see text] The efficient construction of an ingenol intermediate exhibiting "insideminus signoutside" intrabridgehead stereochemistry is reported. The sequence features the net conversion of a cis-intrabridgehead compound into a highly strained trans-species via palladium-mediated isomerization of an allylic epoxide followed by a low-temperature alkoxide-accelerated 1,5-hydrogen migration.
authors.affiliation: Department of Chemistry, Wayne State University, Detroit, Michigan 48202-3489, USA. jhr@chem.wayne.edu
authors.forename: James H
authors.initials: JH
authors.lastname: Rigby
authors.forename: Bérangère
authors.initials: B
authors.lastname: Bazin
authors.forename: J Hoyt
authors.initials: JH
authors.lastname: Meyer
authors.forename: Farahnaz
authors.initials: F
authors.lastname: Mohammadi
mesh_terms: D001952:Bridged-Ring Compounds; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001952:Bridged-Ring Compounds; D004224:Diterpenes; D004852:Epoxy Compounds; D010165:Palladium; C008125:ingenol