Synthesis and crystal structure of axial chiral-chiral oxazoliline ligands  

轴手性-手性噁唑啉配体的合成及其晶体结构

作　　者：YANG Wendeng YANG Fa LIANG Zhengyun WANG Yin XIE Meijie WU Guixian CHEN Minghua 杨文灯;杨发;梁正云;王银;谢美洁;吴贵宪;陈明华(兴义民族师范学院生物与化学学院,贵州兴义562400;黔西南民族职业技术学院医药系,贵州兴义562400)

机构地区：[1]School of Biology and Chemistry,Minzu Normal University of Xingyi,Xingyi 562400,China [2]Department of Medicine,Southwest Guizhou Vocational Technical College for Nationalities,Xingyi 562400,China

出　　处：《分子科学学报》2024年第4期348-352,共5页Journal of Molecular Science

基　　金：supported by Guizhou Province College Students Innovation Project(S202310666114);the Student Program of Minzu Normal University of Xingyi(23XYXS28);Guizhou Province Qianxinan Prefecture Science and Technology Bureau project(2022-1-24).

摘　　要：Seven 2,2'-bipyridine-based oxazole derivatives have been synthesized through multi-step reactions using 2,2'-bipyridine-3,3'-dicarboxylic acid as raw material.The structures of compounds 1-6 were characterized by using 1H NMR,13C NMR,MS,and X-ray single crystal diffraction techniques.The results indicate that only axially chiral enantiomers were observed in the single crystal structures of products 1 and 3 synthesized from achiral amino alcohols;Using racemic amino alcohol((±)-2-aminopropanol)as the raw material,only axial chiral isomers were observed in the single crystal structure of product 2,and no racemic isomer was found.The crystal structure of product 4 based on chiral amino alcohol((S)-valinol)contains non axial chiral isomers and S-type isomers.However,the other two optically pure amino alcohols((S)-phenylpropanol,(R)-phenylpropanol)can only obtain optically pure axially chiral and chiral products 5 and 6,respectively,maintaining the configuration of the raw amino alcohol and no non axial chiral isomer is observed.The product using(±)-2-aminobutanol as the raw material cannot be determined for its absolute configuration as a single crystal of the product has not been obtained.以2,2'-联吡啶-3,3'-二甲酸为原料,经多步反应合成了7种2,2'-联吡啶基轴手性-手性噁唑啉衍生物,并采用1H NMR,13C NMR,MS和X-射线单晶衍射技术对化合物1-6结构进行了表征。单晶结构表明:使用无手性氨基醇,合成的产物1和3的单晶结构中仅见轴手性异构体;使用外消旋氨基醇((±)-2-氨基丙醇)作为原料,所得产物2的单晶结构中仅见轴手性-手性异构体,而未见内消旋体;基于手性氨基醇((S)-缬氨醇)的产物4的晶体结构中仅有非轴手性异构体和S型异构体;分别使用手性氨基醇((S)-苯丙氨醇、(R)-苯丙氨醇)得到的产物5和6的晶体结构中都只有一种轴手性异构体,保持了原料氨基醇的构型,未见非轴手性异构体。使用(±)-2-氨基丁醇作为原料的产物,因为没有得到其产物的单晶,无法确定它的绝对构型。

关 键 词：2 2'-bipyridine-3 3'-dicarboxylic acid chiral β-aminoalcohols axial chiral compound axial chiral-chiral oxazoline ligand crystal structure 

分 类 号：O626[理学—有机化学] O76[理学—化学]