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Towards Stereochemical Control" Two Approaches for the Highly anti.Diastereoselective Construction of the Spirolactone Moieties of Some Stemona Alkaloids
  • ISSN号:1001-604X
  • 期刊名称:《中国化学:英文版》
  • 时间:0
  • 分类:O629.3[理学—有机化学;理学—化学] O623.542[理学—有机化学;理学—化学]
  • 作者机构:[1]Department of Chemistry and Fujian Provincial Key Laboratory for Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
  • 相关基金:Acknowledgement The authors are grateful for financial support from the National Basic Research Program (973 Program) of China (Grant No. 2010CB833200), the NSF of China (21072160; 20832005), the Fundamental Research Funds for the Central Universities of China (Grant No. 201112G001).
中文摘要:

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。

英文摘要:

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.

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期刊信息
  • 《中国化学:英文版》
  • 主管单位:
  • 主办单位:中国化学会
  • 主编:
  • 地址:上海市枫林路354号中科院上海有机化学研究所
  • 邮编:200032
  • 邮箱:
  • 电话:021-54925243
  • 国际标准刊号:ISSN:1001-604X
  • 国内统一刊号:ISSN:31-1547/O6
  • 邮发代号:4-646
  • 获奖情况:
  • 中国期刊方阵“双高”期刊
  • 国内外数据库收录:
  • 美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,英国英国皇家化学学会文摘
  • 被引量:175