title: Total synthesis of the biphenyl alkaloid (-)-lythranidine.
abstract: A sequence comprising a ring-closing alkyne metathesis of a propargyl alcohol derivative, followed by a ruthenium-catalyzed redox isomerization of the derived cycloalkyne and a transannular aza-Michael addition allowed the formation of the distinguishing piperidine-metacyclophane framework of the Lythraceum alkaloid lythanidine in a few high-yielding steps. This application attests to the excellent functional-group tolerance of a molybdenum alkylidyne complex endowed with triphenylsilanolate ligands, which enabled the macrocyclization even in the presence of protic functionalities, and thus illustrates the power of contemporary catalytic acetylene chemistry for target-oriented synthesis.
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany).
authors.forename: Konrad
authors.initials: K
authors.lastname: Gebauer
authors.forename: Alois
authors.initials: A
authors.lastname: Fürstner
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry
chemical_list: D000470:Alkaloids; C032336:lythranidine; D012428:Ruthenium
keywords: 1,4 additions; alkynes; metathesis; molybdenum; ruthenium