Enantioanalysis of Some Chiral Compounds in Asymmetric Synthesis of Tetramate-related Natural Products by High Performance Liquid Chromatography

手性是自然界普遍存在的现象，手性化合物（单一对映体）在药物、天然产物、农业化学和液晶材料等许多领域都具有广泛应用。不对称合成（即手性合成）是获得单一对映体最直接有效的方法，其中单一对映体光学纯度是判断不对称合成反应价值的重要参数。因此，对映体纯度的测定是不对称合成研究中重要的分析测定问题。 手性色谱法是目前公认最可靠、准确测定对映体纯度的方法之一，特别是手性固定相高效液相色谱法以其直接、立体选择性好和适应性强等优点在手性色谱中最具优势。本论文围绕含特特拉姆酸酯结构的海洋天然产物不对称合成研究中的若干重要手性中间体化合物分离和对映体纯度分析问题，开展手性高效液相色谱应用研究。如对于缺少强紫外吸...Chirality widely exists in our world. Chiral compounds (single enantiomers) have comprehensive applications in many fields dealing with pharmaceuticals, natural products, agrochemicals, and ferroelectric liquid crystals etc. Asymmetric synthesis is the most effective and straightly method for obtaining the single enantiomer. The enantiomeric purity which is used to estimate the value of the asymme...学位：理学硕士院系专业：化学化工学院化学系_分析化学学号：1912005130181

HPLC Enantioseparation of Methyl 5-Ethyloxylcarbonyltetramate and 5-Ethyloxylcarbonyl-4-hydroxy-2-pyrrolidinone

合成了外消旋5-乙氧基羰基特特拉姆酸甲酯(1)和顺/反式5-乙氧基羰基-4-羟基-2-吡咯烷酮(2),并利用手性高效液相色谱制备少量的单一对映体标样进行圆二色光谱表征。在此基础上,系统研究了这3对外消旋体化合物在Chiralpak AD-H和Chiralcel OD-H手性柱上的液相色谱拆分行为和对映体出峰顺序。采用正己烷-异丙醇(体积比60∶40)作流动相,外消旋化合物1在Chiralpak AD-H柱上得到很好的拆分,k1、α和RS分别为0.99、2.65和12.5;采用正己烷-异丙醇(体积比80∶20)作流动相,化合物2的4个立体异构体可以同时在Chiralpak AD-H柱上得到基线分离,反式-2对映体的k1、α1和RS1分别为1.69、1.12和1.56,顺式-2对映体的k、α和R分别为2.58、1.16和2.28。Racemic methyl 5-ethyloxylcarbonyltetramate(1)and trans/cis-5-ethyloxylcarbonyl-4-hydroxy-2-pyrrolidinone(2) were synthesized.The single enantiomer of compound 1 and 2 was prepared by chiral HPLC and characterized by CD.The chromatographic behaviors and enantiomer elution order of these compounds were investigated on the Chiralpak AD-H and Chiralcel OD-H columns in normal phase mode.A good resolution of racemic compound 1 was obtained on the Chiralpak AD-H column with n-hexane/2-propanol(60∶40,by volume)as mobile phase,the values of α and RS were 2.65 and 12.5 respectively.A baseline separation of four stereoisomers of the racemate 2 was also obtained on the Chiralpak AD-H column with n-hexane/2-propanol(80∶20,by volume)as mobile phase.The values of α1 and α2 were 1.12 and 1.16 respectively for trans-2 and cis-2.国家自然科学基金资助项目(20572088);; 福建省自然科学基金资助项目(C0510001

Determination of Enantiomeric Purity of 1-Trimethylsilyl-1-decyn-3-ol by Chiral HPLC

以苯甲酰氯试剂衍生1-三甲基硅基-1-炔-3-癸醇,得到具有强紫外吸收的1-三甲基硅基-1-癸炔-3-苯甲酸酯.考察流动相中不同醇调节剂、乙醇含量和柱温对外消旋1-三甲基硅基-1-癸炔-3-苯甲酸酯对映体在Chiralcel OD-H手性柱上色谱分离的影响,建立测定1-三甲基硅基-1-炔-3-癸醇对映体纯度的色谱分析方法.结果表明:以正己烷-乙醇(99.950.05,体积比)为流动相,检测波长为228nm,外消旋苯甲酰氯衍生对映体在Chiralcel OD-H柱上得到很好的分离,保留时间分别为6.94min和8.11min,分离因子和分辨率分别为1.41和3.75.本法灵敏度高,方法简便,适合于手性1-三甲基硅基-1-炔-3-癸醇样品的对映体纯度分析.A simple and accurate method for determination of the enantiomeric purity of 1-trimethylsilyl-1-decyn-3-ol by chiral high-performance liquid chromatography was established.The 1-decyn-3-ol enantiomers were derivatized with benzoyl chloride by esterification to the benzoates,which could be detected sensitively by an UV monitor.The racemic 3-benzoyloxy -1-trimethylsilyl-1-decyne was completely resolved on Chiralcel OD-H column using n-hexane-ethanol (99.95:0.05,by vol.) as mobile phase in 9 minutes,the values of α and RS were 1.41 and 3.75 respectively.The effects of different alcohol modifiers and ethanol percentage in mobile phase,as well as column temperature on chiral separation of the benzoate derivatives were discussed.Precision,linearity and limit of detection of the chromatographic method were also evaluated.福建省自然科学基金(C0510001);; 国家基础科学人才培养基金(J0630429)资