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Efficient synthesis and resolution of meta-substituted inherently chiral aminocalix[4]arene derivatives
  • ISSN号:0251-0790
  • 期刊名称:《高等学校化学学报》
  • 时间:0
  • 分类:O621.34[理学—有机化学;理学—化学] TQ028.5[化学工程]
  • 作者机构:[1]Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • 相关基金:This paper is dedicated to Professor LIU YouCheng on the occasion of his 90th birthday. This work was supported by the National Natural Science Foundation of China (20625206), the National Basic Research Program of China (2008CB617501, 2009ZX09501-018), and the Chinese Academy of Sciences.
中文摘要:

有效合成和分辨率一系列代替元内在地 chiral aminocalix [4 ] arene 衍生物被描述了。因而, meta-nitro, bromo 和 chloro 内在地代替了 chiral 杯[4 ] arenes 能被 aminocalix 的 acylating 产品的硝代, bromination,和氯化直接综合[4 ] arene。meta-Cyano 和苯基内在地代替了 chiral aminocalix [4 ] arenes 被亲核的替换反应乐意地获得或从 meta-bromo 联合反应的铃木在催化 Pd 的条件下面代替了一个。为运动分辨率外消旋内在地 chiral aminocalix [ 4 ] arenes ,取代者的撤退电子的能力对改进 acylation 进程的分辨率效率有用,这被发现,并且运动分辨率能高效地被用于内在地代替的 meta-nitro 的分辨率 chiral aminocalix [ 4 ] arene ,提供( cS )-或( cR )在多达95%或99.9% ee 价值的异构体,分别地与相应 chiral acylating 试剂。而且,由 chiral 的介绍辅助, meta-cyano 和苯基的 enantiopure 相对极内在地代替了 chiral aminocalix [4 ] arenes 能乐意地也被获得。这些 enantiopure aminocalix [4 ] arenes 是为构造新奇 chiral 受体和不对称的催化剂的潜在的积木。

英文摘要:

Efficient synthesis and resolution of a series of meta-substituted inherently chiral aminocalix[4]arene derivatives have been de- scribed. Consequently, the meta-nitro, bromo and chloro substituted inherently chiral calix[4]arenes could be directly synthesized by the nitration, bromination, and chlorination of the acylating product of aminocalix[4]arene, meta-Cyano and phenyl substituted inherently chiral aminocalix[4]arenes were readily obtained by the nucleophilic substitution reaction or Suzuki coupling reaction from the meta-bromo substituted one under the Pd-catalyzed conditions. For kinetic resolution of the racemic inherently chiral aminocalix[4]arenes, it was found that the electron-withdrawing ability of substituent was helpful to improving the resolution efficiency of the acylation process, and the kinetic resolution could be efficiently applied to the resolution of meta-nitro substi- tuted inherently chiral aminocalix[4]arene, providing (cS)- or (cR)-isomer in up to 95% or 99.9% ee value, respectively, with the corresponding chiral acylating reagent. Moreover, by introduction of the chiral auxiliary, enantiopure antipodes of meta-cyano and phenyl substituted inherently chiral aminocalix[4]arenes could also be readily obtained. These enantiopure amino- calix[4]arenes are potential building blocks for constructing novel chiral receptors and asymmetric catalysts.

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期刊信息
  • 《高等学校化学学报》
  • 北大核心期刊(2011版)
  • 主管单位:中华人民共和国教育部
  • 主办单位:吉林大学 南开大学
  • 主编:周其凤
  • 地址:吉林大学南胡校区
  • 邮编:130012
  • 邮箱:cjcu@jlu.edu.cn
  • 电话:0431-88499216
  • 国际标准刊号:ISSN:0251-0790
  • 国内统一刊号:ISSN:22-1131/O6
  • 邮发代号:12-40
  • 获奖情况:
  • 首届及第二届国家期刊奖,连续两届“百种中国杰出学术期刊”,中国期刊方阵“双高”期刊
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  • 被引量:50676