Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen.
Org Lett. 2010 Aug 6;12(15):3418-21. doi: 10.1021/ol1012185.
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.
通过 Rh(2)(OAc)(4)催化的反应，从重氮酮前体生成了具有反稠合环戊烷环的环状羰基叶立德，并与烯丙基丙炔酸酯捕获。1,3-偶极环加成导致立体选择性地形成了氧桥连的多环化合物。通过 Curtius 降解，环加成产物转化为倍半萜类愈创木烷内酯家族的典型环骨架。
