title: Synthesis of the guaianolide ring system via cycloaddition of a bicyclic carbonyl ylide with allyl propiolate.
abstract: A cyclic carbonyl ylide with a trans-annulated cyclopentane ring was generated by a Rh(2)(OAc)(4)-catalyzed reaction from a diazoketone precursor and trapped with allyl propiolate. The 1,3-dipolar cycloaddition led to the stereoselective formation of an oxygen-bridged polycycle. Via Curtius degradation, the cycloadduct was transformed to the ring skeleton typical of the sesquiterpene family of guaianolides.
authors.affiliation: Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen.
authors.forename: Vaidotas
authors.initials: V
authors.lastname: Navickas
authors.forename: Dmitry B
authors.initials: DB
authors.lastname: Ushakov
authors.forename: Martin E
authors.initials: ME
authors.lastname: Maier
authors.forename: Markus
authors.initials: M
authors.lastname: Ströbele
authors.forename: H-Jürgen
authors.initials: HJ
authors.lastname: Meyer
mesh_terms: D002384:Catalysis; D003500:Cyclization; D003517:Cyclopentanes / Q000737:chemistry*; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D045789:Sesquiterpenes, Guaiane / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D003517:Cyclopentanes; D045789:Sesquiterpenes, Guaiane; D012238:Rhodium