title: Asymmetric synthesis of cis-7-methoxycalamenene via the intramolecular Buchner reaction of an α-diazoketone.
abstract: The asymmetric synthesis of cis-7-methoxycalamenene 1 has been accomplished using the intramolecular Buchner reaction of α-diazoketone 7 as the key step in the synthetic route. Upon reduction of the equilibrating azulenone structure 8, the resulting azulenol 9 rearranges to dihydronaphthalene 10 containing the 6,6-membered bicyclic ring system characteristic of 1, by means of an acid-catalyzed aromatization process. Transformation of 10 to 1 is accomplished through a three-step reaction sequence.
authors.affiliation: Department of Chemistry, Analytical and Biological Chemistry Research Facility, University College Cork, Cork, Ireland.
authors.forename: Paul A
authors.initials: PA
authors.lastname: McDowell
authors.forename: David A
authors.initials: DA
authors.lastname: Foley
authors.forename: Patrick
authors.initials: P
authors.lastname: O'Leary
authors.forename: Alan
authors.initials: A
authors.lastname: Ford
authors.forename: Anita R
authors.initials: AR
authors.lastname: Maguire
mesh_terms: D052176:Azulenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis*
chemical_list: D052176:Azulenes; D007659:Ketones; D009281:Naphthalenes; D012717:Sesquiterpenes; D013729:Terpenes; C572570:cis-7-methoxycalamenene