联二萘酚手性溶剂化试剂鉴定黄烷酮类天然产物手性的研究

Identification of chirality of flavanone natural products by bis(dinaphthyl)phenol chiral solvating agents

目的手性黄烷酮类天然产物存在于多种中药材或食品中,有多样化的生物活性,是具有重要研究价值的药物先导化合物。本研究探讨如何高效、经济地鉴定黄烷酮类天然产物的手性。方法以联二萘酚(binaphthol,BINOL)类化合物作为手性溶剂化试剂(chirul solvating agents,CSA),选择9种含ABX自旋耦合系统的黄烷酮类天然产物作为待测底物,通过核磁共振测试氢谱的变化进行手性识别,并计算其对映体过量值(enantiomeric excess,ee),再选择其中4种样品进行高效液相色谱(high performance liquid chromatography,HPLC)手性拆分,激发态圆二色谱(exciton circular dichroism,ECD)绝对构型测试。结果9种样品加入S型BINOL均能够通过核磁共振氢谱进行识别,并计算出ee值。4种样品通过HPLC能够拆分为8个对映异构单体,均能通过ECD判定出绝对构型,证明4种样品是鲜屑混合物。结论在核磁共振氢谱中,运用BINOL溶剂化试剂能够经济、高效地识别含ABX自旋耦合系统黄烷酮类天然产物的手性,判断其是否为天然来源的鲜屑混合物,并计算出ee值。

Objective Chiral flavanone natural products exist in various Chinese medicinal herbs or foods,with diverse biological activities,and are important lead compounds for drug research.This study explored how to efficiently and economically identify the chirality of natural products of flavanones.Methods Binaphthol(BINOL)compounds were used as chiral solvating agents,and 9 natural products of flavanones containing ABX spin coupling systems were selected as test substrates.The changes in hydrogen spectra were detected by nuclear magnetic resonance for chiral recognition,and the enantiomeric excess(ee)values were calculated.Four of the samples were then selected for high performance liquid chromatography(HPLC)chiral separation,and excited circular dichroism(ECD)absolute configuration testing.Results Nine samples added to S-type BINOL can be identified by nuclear magnetic resonance hydrogen spectroscopy and ee values can be calculated.Four samples can be separated into eight enantiomers by HPLC,and their absolute configurations can be determined by ECD,proving that the four samples are a mixture of scalemic mixture.Conclusion In nuclear magnetic resonance hydrogen spectroscopy,the use of BINOL solvent reagents can economically and efficiently identify the chirality of natural products containing ABX spin coupled system flavanones,determine whether they are natural source scalemic mixtures,and calculate ee values.