属于 tuberostemospironine 组的一些 Stemona 碱与反配置(C-9/C-9a ) 拥有 spirolactone 一半。在这份报纸,我们描述二条途径到这结构的统一。由把溴原子用作一个无踪迹的指导组,酉同类 6 的调停 SmI2 的减少的联合和 -bromomethacrylate 继续了完全的 anti-diastereoselectivity。(chelation ) 当指导不在时组织,从与从 bromomethacrylate 产生的 organozinc 试剂的酒精 15 导出的酉同类的一个壶反应负担得起 spiro -- 甲又 -- 作为单个 diastereomer 的内酯衍生物 16。这二高度, diastereoselective 方法将在包含设置反的 spiro-lactone/pyrrolidine 一半的 stemona 碱的合成发现申请。另外根据我们的以前的工作,全部的合成()-9-epi-11-demethylsessilifoliamide J (11 ) ,和改进合成()-9,11-di-epi-sessilifoliamide J (9 ) 被完成。
Some Stemona alkaloids belonging to the tuberostemospironine group possess a spirolactone moiety with anti-configuration (C-9/C-9a). In this paper, we describe two approaches to this structural unity. By using bromine atom as a traceless directing group, the SmI2-mediated reductive coupling of ketone 6 and fl-bromomethacrylate proceeded with complete anti-diastereoselectivity. In the absence of an a-directing (chelation) group, the one-pot reaction of the ketone derived from alcohol 15 with the organozinc reagent generated from bromomethacrylate af- forded spiro-a-methylene-y-lactone derivative 16 as a single diastereomer. These two highly diastereoselective methods would find application in the synthesis of stemona alkaloids containing anti-configured spiro-lactone/pyr- rolidine moieties. In addition, on the basis of our previous work, the total synthesis of (-)-9-epi-11-demethyl- sessilifoliamide J (11), and an improved synthesis of (-)-9,11-di-epi-sessilifoliamide J (9) were accomplished.