Terpenoids from the Roots of Ligularia muliensis

Three new eremophilane‐type sesquiterpenes, (6β,8α)‐6‐(acetyloxy)‐8‐hydroxyeremophil‐7(11)‐en‐12,8‐olide ( 1 ), (6α,8α)‐6‐hydroxyeremophil‐7(11)‐en‐12,8‐olide ( 2 ), and (6α,8α)‐6‐(acetyloxy)eremophil‐7(11)‐en‐12,8‐olide ( 3 ) ((8α)‐eremophil‐7(11)‐en‐12,8‐olide = (4aR,5S,8aR,9aS)‐4a,5,6,7,8,8a,9,9a‐octahydro‐3,4a,5‐trimethylnaphtho[2,3‐b]furan‐2(4H)‐one), besides the recently elucidated eremoligularin ( 4 ) and bieremoligularolide ( 5 ), as well as a new highly oxygenated monoterpene, rel‐(1R,2R,3R,4S,5S)‐p‐menthane‐1,2,3,5‐tetrol ( 12 ), together with six known constituents, i.e., the sesquiterpenes 6 and 7 , the norsesquiterpenes 8 – 10 , and the monoterpene 13 , were isolated from the roots of Ligularia muliensis. In addition, an attempt to dimerize 1 to a bieremophilenolide (Scheme) resulted in the generation of the new derivative (6β,8β)‐6‐(acetyloxy)‐8‐chloroeremophil‐7(11)‐en‐12,8‐olide ( 11 ). The new structures were established by means of detailed spectroscopic analysis (IR, FAB‐, EI‐, or HR‐ESI‐MS as well as 1D‐ and 2D‐NMR experiments). Compounds 4 and 5 were evaluated for their antitumor effects in vitro (Table 3).     

Chemical and Genetic Study of Ligularia cyathiceps in Yunnan Province of China

Root chemicals and evolutionarily neutral DNA regions in L. cyathiceps samples collected in the Zhongdian (Shangrila) County of Yunnan, P. R. China, were examined. Twenty compounds were isolated, including three new ones, 1β,10β‐epoxy‐6β‐(propionyloxy)furanoeremophilan‐9‐one ( 6 ), 1β,10β‐epoxy‐8α‐ethoxyeremophila‐6,11‐diene ( 14 ), and 11αH‐6β‐isobutyryloxy‐1β,10β,7β,8β‐diepoxyeremophilan‐12,8α‐olide ( 15 ). The chemical diversity was found to be limited, with cacalol ( 1 ) and 6‐(acyloxy)furanoeremophilan‐9‐ones ( 4 and/or 5 ) being major components in all the samples. The nuclear ribosomal RNA gene was also found to harbor little variation, although two distinct sequence types were found for the plastid atpB‐rbcL intergenic region.     

Diversity of Ligularia kanaitzensis in sesquiterpenoid composition and neutral DNA sequences

Twenty-six eremophilane-type sesquiterpenoids, including six new compounds, were isolated from the title species. One of the new compounds, kanaitzensol, suggested the presence of an enzyme for the conversion of eremophil-7(11)-en-8-one derivative to furanoeremophilanes. The plant was collected at 15 locations in Yunnan Province of China and found to be diverse with respect to its sesquiterpenoid composition. DNA sequencing also revealed a large intraspecific diversity of the plant.     

Application of high-speed counter-current chromatography for the isolation of antiviral eremophilenolides from Ligularia atroviolacea

Ligularia is mainly distributed in the western regions of China. Most of the species have been traditionally used in folk medicine for the treatment of hepatitis B, asthma, hemoptysis and pulmonary tuberculosis. In our continuation of research on antiviral components from traditional Chinese medicine, Ligularia atroviolacea was tested for inhibitory effects on hepatitis B virus (HBV). A bioassay-guided phytochemical examination of L. atroviolacea disclosed that its ethyl acetate extract, which was made up of two eremophilenolides, showed suppressive activity on the expression of HBV surface antigen (HBsAg) in the HepG2.2.15 cell line. Then a simple and effective preparative high-speed counter-current chromatography method was successfully developed for the isolation and purification of two main active metabolites, 8beta-hydroxyeremophil-3,7(11)-dien-12,8alpha;15,6alpha-diolide and 8beta-methoxyeremophil-3,7(11)-dien-12,8alpha;15,6alpha-diolide from the ethyl acetate extract of L. atroviolacea by a one-step separation using a two-phase solvent system composed of light petroleum (60-90 degrees C)-ethyl acetate-methanol-water (9:1:8:2, v/v/v). The chemical structures of the two eremophilenolides were identified by ESI-MS, (1)H-NMR and (13)C-NMR analysis. The anti-HBV activity of the two purified compounds was measured; both of them showed suppressive activity on the expression of HBsAg in the HepG2.2.15 cell line. The results support the continued and expanded exploitation and utilization of L. atroviolacea. Copyright (c) 2008 John Wiley & Sons, Ltd.     

8β-hydroxyeremophil-7(11)-ene-12,8α(4β,6α)-diolide分子的晶体结构

运用层析法、结晶法从狭苞橐吾全草中分离得到艾里莫芬烷型倍半萜8β-hydroxyeremophil-7(11)-ene-12,8α(4β,6α)-diolide化合物,并通过质谱、核磁共振氢谱和碳谱、氢核-氢核相关谱、异核多量子相干谱和异核多键相干谱进行结构鉴定．其单晶经X射线衍射测试表明,其晶体属正交晶系,空间群为P212121,晶胞参数为: a=6．8519(5),b=10．7191(8),c=18．5942(14)A,V=1365．67(18) A3,Z=4,Dc=1．354 mg／m3．F(000)=592,μ=0．101 mm-1     

A new 8-O-4′-type neolignan from Ligularia narynensis

A new 8-O-4′-type neolignan named narynenol （1） was isolated from the roots of Ligularia narynensis. Its structure and the relative configurations were confirmed by spectroscopic data interpretation. 2007 Zhong Jian Jia. Published by Elsevier B.V. on behalf of Chinese Chemical Society, All rights reserved.     

Two New Sesquiterpenes from Ligularia macrophylla

Two new eremophilane sesquiterpenes, 15β-formic ether-6-oxo-furanoeremophilane （1） and 6α, 15β-epoxy eremophila-7（11）-en-8α, 12-olide （2） were isolation from the roots of Ligularia macrophylla. Their structures were deduced from spectroscopic methods and 2D NMR experiments.     

Bieremoligularolide and eremoligularin, two novel sesquiterpenoids from Ligularia muliensis

From the roots of Ligularia muliensis, a novel bieremophilanolide and a new eremophilanolide have been isolated and their structures were elucidated by spectroscopic techniques, including HRMS, IR, UV, 1D-NMR, 2D-NMR, and CD spectra.     

A New Stigmasterol and a New Eremophilenolide from Ligularia dolichobotrys

A new stigmasterol 3β, 7α, 22-trihydoxystigmast-5-ene (1) and a new eremophilenolide 8α-methoxy-6β-angeloyloxyeremophil-7(1 l)-en-8β, 12-olide-14-oic acid (2) were isolated from Ligularia dolichobotrys Diels. Their structures were deduced on the basis of spectral data.     

Three New Bisabolane Sesquiterpenes from Ligularia songarica

Three new bisabolane sesquiterpenes, songaricalarins F–H ( 1 – 3 , resp.), and five known analogs, 4 – 8 , were isolated from roots and rhizomes of Ligularia songarica. The structures were elucidated by spectroscopic methods, including 2D‐NMR techniques. The isolated compounds were also evaluated for their cytotoxic activities, against human lung carcinoma (A‐549) and human breast adenocarcinoma (MCF‐7) cell lines, and three compounds were found to show moderate cytotoxicities.