Efficient synthesis and resolution of meta-substituted inherently chiral aminocalix[4]arene derivatives  

作　　者：XU ZhenXiang ZHANG Chun HUANG ZhiTang CHEN ChuanFeng 

机构地区：[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

出　　处：《Chinese Science Bulletin》2010年第25期2859-2869,共11页

基　　金：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

摘　　要：Efficient synthesis and resolution of a series of meta-substituted inherently chiral aminocalix[4]arene derivatives have been described. 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 substituted 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.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.

关 键 词：芳烃衍生物 手性助剂 高效合成 杯[4]芳烃 动力学拆分 亲核取代反应 酰化试剂 苯基取代 

分 类 号：O621.34[理学—有机化学] TQ028.5[理学—化学]