当归头水提取物中木脂素类对映体的分离、手性拆分和绝对构型确定

Isolation, chiral separation and absolute configuration determination of lignanoids from an aqueous extract of the Angelica sinensis root head

摘要: 通过不同型号树脂、正和反相硅胶及各种凝胶柱色谱, 结合反相和手性柱HPLC技术, 从“归头”水煎提取物中分离并手性拆分得到9对木脂素类对映体, 其中3对新结构对映体(+)-/(-)-1~(+)-/(-)-3 以及2对首次实现手性拆分的对映体(+)-/(-)-4和(+)-/(-)-5。通过波谱数据分析、电子圆二色谱(ECD) 理论计算和X-单晶衍射技术, 确定了所有对映体的绝对构型。新结构和首次拆分并确定绝对构型的对映体分别命名为(+)-/(-)-当归木脂素Q~T (+)-/(-)-1~(+)-/(-)-4 和(+)-/(-)-滇瑞香醇(+)-/(-)-5。

Abstract: From an aqueous extract of the Angelica sinensis root head (guitou), nine pairs of lignanoid enantiomers (+)-/(-)-1-(+)-/(-)-9, including three pairs of new structures (+)-/(-)-1-(+)-/(-)-3 and two pairs of chiral separated enantiomers for the first time (+)-/(-)-4 and (+)-/(-)-5, were isolated and chirally separated by column chromatography over different types of resin, normal and reversed phase silica gels, together with HPLC techniques using reversed phase and chiral columns. Their structures were determined by spectroscopic data analysis, theoretic calculation of electronic circular dichroism (ECD) spectra, and single-crystal X-ray diffraction. The chiral separated new enantiomers named (+)-/(-)-angelignanins Q-T (+)-/(-)-1-(+)-/(-)-4 and (+)-/(-)-daphneresinol (+)-/(-)-5, respectively.