Thornton Paul D, Burnell D Jean
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3.
Org Lett. 2006 Jul 20;8(15):3195-8. doi: 10.1021/ol0609715.
[Structure: see text] The carbocyclic ring system of the aquariolide diterpenes has been synthesized by two routes involving a diastereoselective Pauson-Khand reaction and subsequent ring expansion. In one route, a tetracyclic enone was elaborated to generate the nine-membered ring by Grob fragmentation. In the second approach, a spirocyclic tricycle underwent a facile anionic oxy-Cope rearrangement to complete the synthesis of the desired ring system.
[结构：见正文] 通过两条路线合成了水族内酯二萜的碳环系统，这两条路线涉及非对映选择性的Pauson-Khand反应及随后的扩环反应。在一条路线中，通过格罗布碎裂反应将四环烯酮进行修饰以生成九元环。在第二条路线中，螺环三环化合物经历了容易进行的负离子氧杂-Cope重排反应，从而完成了所需环系统的合成。
