title: Mechanistic diversity of the van Leusen reaction applied to 6-ketomorphinans and synthetic potential of the resulting acrylonitrile substructures.
abstract: Tosylmethyl isocyanide was used to convert 7,8-didehydro-6-ketomorphinans to 6,7-didehydromorphinan-6-carbonitriles with retainment of the 4,5-epoxy ring. However, ring opening occurred in the presence of NaH giving 5,6,7,8-tetradehydromorphinan-6-carbonitriles. Addition of nucleophiles such as Li diisopropylamide or Grignard reagents to the acrylonitrile substructure yielded ring-opened 5,6-didehydro products. Seven products were characterized by X-ray crystal structure analysis and revealed insight into the mechanistic diversity of the van Leusen reaction.
authors.affiliation: Department of Pharmaceutical Chemistry, Institute of Pharmacy and Center for Molecular Biosciences Innsbruck, University of Innsbruck, 6020 Innsbruck, Austria.
authors.forename: Johannes
authors.initials: J
authors.lastname: Schütz
authors.forename: Petra
authors.initials: P
authors.lastname: Windisch
authors.forename: Elka
authors.initials: E
authors.lastname: Kristeva
authors.forename: Klaus
authors.initials: K
authors.lastname: Wurst
authors.forename: Karl-Hans
authors.initials: KH
authors.lastname: Ongania
authors.forename: Ulrike E I
authors.initials: UE
authors.lastname: Horvath
authors.forename: Herwig
authors.initials: H
authors.lastname: Schottenberger
authors.forename: Gerhard
authors.initials: G
authors.lastname: Laus
authors.forename: Helmut
authors.initials: H
authors.lastname: Schmidhammer
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D015394:Molecular Structure; D009019:Morphinans / Q000138:chemical synthesis / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D009019:Morphinans; D009570:Nitriles