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。
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.