Bülow N, Konig W A
Institut für Organische Chemie, Universität Hamburg, Germany.
Phytochemistry. 2000 Sep;55(2):141-68. doi: 10.1016/s0031-9422(00)00266-1.
Germacrene D is considered as a precursor of many sesquiterpene hydrocarbons. We have investigated the acid catalyzed as well as the photochemically and thermally induced rearrangement processes of germacrene D isolated from several Solidago species, which contain both enantiomers of germacrene D. Enantiomeric mixtures of sesquiterpenes of the cadinane, eudesmane (selinane), oppositane, axane, isodaucane, and bourbonane group as well as isogermacrene D were identified as main products and made available as reference compounds for structure investigations and stereochemical assignments of plant constituents. Delta-amorphene, one of the rearrangement products, was identified as a natural product for the first time. The absolute configuration of gamma-amorphene was revised by correlation with the absolute configuration of germacrene D. The mechanisms of the rearrangement reactions are discussed.
吉马烯 D 被认为是许多倍半萜烃的前体。我们研究了从几种含有吉马烯 D 对映体的一枝黄花属植物中分离出的吉马烯 D 的酸催化、光化学和热诱导重排过程。杜松烷、桉叶烷（芹子烷）、反异丁烷、紫杉烷、异菖蒲烷和波旁烷类倍半萜以及异吉马烯 D 的对映体混合物被鉴定为主要产物，并作为参考化合物用于植物成分的结构研究和立体化学归属。重排产物之一 δ-阿莫尔芬首次被鉴定为天然产物。通过与吉马烯 D 的绝对构型相关联，修正了 γ-阿莫尔芬的绝对构型。讨论了重排反应的机理。
