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'-dihy-droseselin(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.
Abstract
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 1H 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'-dihydrose-selin(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.
基金项目
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)
NETL
NSTL
万方数据