有机化学 ›› 2018, Vol. 38 ›› Issue (7): 1712-1717.DOI: 10.6023/cjoc201801036 上一篇    下一篇

研究论文

Selectfluor介导的高效高选择性地脱除叔丁氧羰基方法研究

曾逸杰a, 段岳a, 赵辉b, 胡祥国a   

  1. a 江西师范大学国家单糖化学合成工程技术研究中心 南昌 330022;
    b 安徽省应用技术研究院 安徽省植物活性成分分离提取工程技术研究中心 合肥 230031
  • 收稿日期:2018-01-25 修回日期:2018-02-12 发布日期:2018-03-16
  • 通讯作者: 赵辉, 胡祥国 E-mail:zh1986@iccas.ac.cn;huxiangg@iccas.ac.cn
  • 基金资助:

    国家自然科学基金(No.21502076)、江西省自然科学基金(No.20161BAB213068)、合肥市百人计划及江西省杰出青年基金(No.20171BCB23039)资助项目.

Efficient and Chemoselective Deprotection of N-t-Butyloxycarbonyl Group Mediated by Selectfluor

Zeng Yijiea, Duan Yuea, Zhao Huib, Hu Xiangguoa   

  1. a National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022;
    b Anhui Engineering Technology Research Center for Extraction and Isolation of Active Components, Anhui Academy of Applied Technology, Hefei 230031
  • Received:2018-01-25 Revised:2018-02-12 Published:2018-03-16
  • Contact: 10.6023/cjoc201801036 E-mail:zh1986@iccas.ac.cn;huxiangg@iccas.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21502076), the Natural Science Foundation of Jiangxi Province (No. 20161BAB213068), the Hundred-Talent Program (Hefei) and the Outstanding Young Talent Program of Jiangxi Province (No. 20171BCB23039).

商品化的selectfluor[即1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)盐]具有不吸潮的特性,是一种被应用得最为广泛的氟代试剂.因此,发现并理解其新的反应特性对于应用该试剂具有非常重要的意义.本工作报道了selectflour可以用于选择性脱除双保护氨基上的一个叔丁氧羰基保护基.该方法具有条件温和、操作简单、化学选择性好等特点.跟其他方法相比,该脱保护方法有一定的应用价值,被成功应用于一系列氨基酸衍生物的脱保护,在医药上合成有潜在用途的嘌呤衍生物.以氘代乙腈为溶剂的核磁反应实验解释了为什么该反应需要等物质的量的selectfluor试剂.

关键词: selectfluor, 叔丁氧羰基, 脱保护, 选择性, 合成

Selectfluor, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo-[2.2.2] octane bis(tetrafluoroborate), is among the most popular fluorinating reagents owning to its commercially availability and non-hygroscopic property. The discovery and understanding of new reactivities of selectfluor are thus important for reaction design and optimization when this popular reagent is employed. It has been found that selectfluor could selectively remove Boc group from doubly protected amines in acetonitrile. This deprotection could be of interest when compared to other reported methods, not only because selectfluor is a solid and easy-to-handle, but also because the reaction is mild, operationally simple and chemoselective. The potential usefulness of this method is demonstrated by the deprotection of a series of protected amino acids and a one-step synthesis of pharmaceutically important purine derivative. The NMR experiments conducted in CD3CN explain why stoichiometric amount of selectfluor is needed for a successful reaction.

Key words: selectfluor, t-butyloxycarbonyl, deprotection, selectivity, synthesis