Synthesis of the guaianolide ring system via cycloaddition of a bicyclic carbonyl ylide with allyl propiolate.
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.
Navickas
Vaidotas
V
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen.
Ushakov
Dmitry B
DB
Maier
Martin E
ME
Ströbele
Markus
M
Meyer
H-Jürgen
HJ
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
D003517:Cyclopentanes; D045789:Sesquiterpenes, Guaiane; D012238:Rhodium