手性色谱-质谱联用导向的前胡中角型吡喃香豆素类化合物分离  

Chiral LC-MS-guided isolation of angular-type pyranocoumarins from Peucedani Radix

作　　者：杨阳 龚兴成 屠鹏飞 刘文静 宋月林 YANG Yang;GONG Xing-cheng;TU Peng-fei;LIU Wen-jing;SONG Yue-lin(Modern Research Center for Traditional Chinese Medicine,Beijing Research Institute of Chinese Medicine,Beijing University of Chinese Medicine,Beijing 102400,China;School of Chinese Materia Medica,Beijing University of Chinese Medicine,Beijing 102400,China;School of Pharmacy,Henan University of Chinese Medicine,Zhengzhou 450046,China)

机构地区：[1]北京中医药大学,北京中医药研究院中药现代研究中心,北京102400 [2]北京中医药大学中药学院,北京102400 [3]河南中医药大学药学院,河南郑州450046

出　　处：《药学学报》2024年第8期2343-2349,共7页Acta Pharmaceutica Sinica

基　　金：中组部“万人计划”-青年拔尖人才;河南中医药大学仲景青年学者项目(00104311-2023-85)。

摘　　要：本研究根据手性色谱-质谱联用导向策略,在利用质谱数据精准识别中药前胡(Peucedani Radix)中角型吡喃香豆素类化合物(angular-type pyranocoumarins, APs)的基础上,采用硅胶、ODS、Sephadex LH-20、非手性(手性)半制备液相色谱等技术从乙酸乙酯部位中共分离得到16个APs,通过1H、13C NMR等技术,分别鉴定为(3′S)-3′-(2-methyl-butyroyl)-4′-oxo-3′, 4′-dihydroseselin(1A)、(3′R)-3′-(2-methyl-butyroyl)-4′-oxo-3′, 4′-dihydroseselin(1B)、(3′S)-3′-isovaleryl-4′-oxo-lomatin(2A)、(3′R)-3′-isovaleryl-4′-oxo-lomatin(2B)、(3′S)-3′-angeloyloxy-4′-oxo-3′, 4′-dihydroseselin (3A)、(3′R)-3′-angeloyloxy-4′-oxo-3′,4′-dihydroseselin (3B)、(3′S,4′S)-白花前胡乙素(4A)、(3′R,4′R)-白花前胡乙素(4B)、(3′S,4′S)-白花前胡素E (5A)、(3′R,4′R)-白花前胡素E (5B)、3′-isovaleryl-4′-angeloyl-cis-khellactone (6)、3′-angeloyl-4′-(2-methyl-butyroyl)-cis-khellactone(7)、(3′S,4′S)-白花前胡甲素(8A)、(3′R,4′R)-白花前胡甲素(8B)、(3′S,4′S)-凯林内酯(9A)和(3′R,4′R)-凯林内酯(9B)。其中,化合物1A、1B为新化合物,化合物2A为已知平面结构的新构型,化合物2A、2B为首次从前胡中分离得到。因此,基于手性LC-MS的成分分析和导向分离,有利于快速发现中药中新化合物,为新颖结构,特别是新的对映异构体的分离提供了有效手段。This study utilized a chiral liquid chromatography-mass spectrometry(LC-MS)-guided isolation strategy to accurately capture angular-type pyranocoumarins(APs)in Peucedani Radix(Chinese name:Qianhu).Sixteen APs were successfully purified from the ethyl acetate extract of Peucedani Radix through deploying various techniques such as silica gel,ODS,Sephadex LH-20,and achiral(chiral)semi-preparative liquid chromatography.After extensive structural measurements,such as^(1)H and 13C NMR spectroscopy,their structures were identified as(3′S)-3′-(2-methyl-butyroyl)-4′-oxo-3′,4′-dihydroseselin(1A),(3′R)-3′-(2-methyl-butyroyl)-4′-oxo-3′,4′-dihydroseselin(1B),(3′S)-3′-isovaleryl-4′-oxo-lomatin(2A),(3′R)-3′-isovaleryl-4′-oxo-lomatin(2B),(3′S)-3′-angeloyloxy-4′-oxo-3′,4′-dihydroseselin(3A),(3′R)-3′-angeloyloxy-4′-oxo-3′,4′-dihydroseselin(3B),(3′S,4′S)-praeruptorin B(4A),(3′R,4′R)-praeruptorin B(4B),(3′S,4′S)-praeruptorin E(5A),(3′R,4′R)-praeruptorin E(5B),3′-isovaleryl-4′-angeloyl-cis-khellactone(6),3′-angeloyl-4′-(2-methyl-butyroyl)-cis-khellactone(7),(3′S,4′S)-praeruptorin A(8A),(3′R,4′R)-praeruptorin A(8B),(3′S,4′S)-khellactone(9A),and(3′R,4′R)-khellactone(9B),respectively.Thereof,compounds 1A and 1B were new compounds,while compound 2A represents a new configuration for a known planar structure.Compounds 2A and 2B were isolated for the first time from Peucedani Radix.Above all,chiral LC-MS-guided isolation strategy is advantageous at rapid capturing new compounds from herbal medicines,providing an effective means for the separation of novel structures,especially new enantiomers.

关 键 词：前胡 化学成分 角型吡喃香豆素 手性色谱-质谱联用导向分离 对映异构体 

分 类 号：R284[医药卫生—中药学]