Hypercohones A-C,acylphloroglucinol derivatives with homo-adamantane cores from Hypericum cohaerens

Three new homo-adamantanyl type natural products were derived from polyprenylated polycyclic acylphloroglucinol.Hypercohones A-C(1-3),along with five other known hypercohones(4-8),were isolated from the aerial parts of Hypericum cohaerens.The structures of 1-3 were elucidated on the basis of comprehensive spectroscopic analysis.The inhibitory activities of these isolates against five human cancer cell lines in vitro were tested.

Hypercohones D–G,New Polycyclic Polyprenylated Acylphloroglucinol Type Natural Products from Hypericum cohaerens

Four new polycyclic polyprenylated acylphloroglucinol type metabolites,hypercohones D–G(1–4),along with four known analogues(5–8),were isolated from the aerial parts of Hypericum cohaerens.The structures of these isolates were elucidated by extensive spectroscopic methods.The inhibitory activities of these isolates against five human cancer cell lines in vitro were also tested.

Carascynol A,a hybrid of caryophyllane-type terpenoid and a C6 unit degraded by polyprenylated acylphloroglucinols from Hypericum ascyron

Carascynol A,an unprecedented 4/9/8 ring system hybrid with a peroxide bridge,was characterized from Hyperi-cum ascyron.The architecture contains a caryophyllane-type moiety and a C_(6) unit derived from polyprenylated acylphloroglucinols.Its structure and absolute configuration were determined by comprehensive spectroscopic and X-ray diffraction data.Biologically,compound 1 inhibited cell proliferation in LoVo,SW480,and HCT116 cell lines(IC_(50)=12.30-24.57μM).

Dearomatized Isoprenylated Acylphloroglucinol Derivatives with Potential Antitumor Activities from Hypericum henryi

A series of dearomatized isoprenylated acylphloroglucinols derivatives,hyperhenols A-E(1-5),as well as seven known analogues(6-12),were characterized from Hypericum henryi.Their structures were determined by combination of NMR,ECD spectroscopy,and X-ray difraction analysis.Compounds 1 and 6-8 were tested to exhibit potential antitumor properties,of which 6 and 7 inhibited cell growth through inducing apoptosis and cell cycle arrest.In addition,these compounds could induce autophagy and PINK1/Parkin-mediated mitophagy in cancer cell lines,as well as suppress lung cancer A549 cells metastasis in vitro.

Anticancer Properties and Mechanism of Action of Oblongifolin C,Guttiferone K and Related Polyprenylated Acylphloroglucinols

Polyprenylated acylphloroglucinols represent an important class of natural products found in many plants.Among them,the two related products oblongifolin C(Ob-C)and guttiferone K(Gt-K)isolated from Garcinia species(notably from edible fruits),have attracted attention due to their marked anticancer properties.The two compounds only differ by the nature of the C-6 side chain,prenyl(Gt-K)or geranyl(Ob-C)on the phloroglucinol core.Their origin,method of extraction and biological properties are presented here,with a focus on the targets and pathways implicated in their anticancer activities.Both compounds markedly reduce cancer cell proliferation in vitro,as well as tumor growth and metastasis in vivo.They are both potent inducer of tumor cell apoptosis,and regulation of autophagy flux is a hallmark of their mode of action.The distinct mechanism leading to autophagosome accumulation in cells and the implicated molecular targets are discussed.The specific role of the chaperone protein HSPA8,known to interact with Ob-C,is addressed.Molecular models of Gt-K and Ob-C bound to HSPA8 provide a structural basis to their common HSPA8-binding recognition capacity.The review shed light on the mechanism of action of these compounds,to encourage their studies and potential development.

Hyparillums A and B: polycyclic polyprenylated acylphloroglucinols from Hypericum patulum

Hyparillums A(1)and B(2),two previously unidentified polycyclic polyprenylated acylphloroglucinols(PPAPs)with intricate architectures,were isolated from Hypericum patulum Thunb.Hyparillum A was the first PPAP with eight-carbon rings based on an unprecedented 6/6/5/6/6/5/6/4 octocyclic system featuring a rare heptacyclo[10.8.1.11,10.03,8.08,21.012,19.014,17]docosane core.In contrast,hyparillum B featured a novel heptacyclic architecture(6/6/5/6/6/5/5)based on a hexacyclo[9.6.1.11,9.03,7.07,18.011,16]nonadecane motif.Furthermore,hyparillums A and B demonstrated promising inhibitory effects on the proliferation of murine splenocytes stimulated by anti-CD3/anti-CD28 monoclonal antibodies and lipopolysaccharide,exhibiting half-maximal inhibitory concentration(IC50)values ranging from 6.13±0.86 to 12.69±1.31μmol·L−1.

Type B polycyclic polyprenylated acylphloroglucinols from the roots of Hypericum beanii

Two new type B polycyclic polyprenylated acylphloroglucinols(PPAPs)(1 and 2)and a known biogenetic precursor hyperbeanol Q(3)were isolated from the root extract of Hypericum beanii,a medicinal plant widespread in southwest China.Their chemical structures were elucidated by 1 D/2 D NMR and HRESIMS data analysis,and absolute configurations were determined through detailed electric circular dichroism(ECD)analysis including ECD exciton chirality,Mo2(OAc)4-induced ECD,and ECD comparison.Of these compounds,hyperbeone A(1)is a typical[3.3.1]-type B PPAP with an unusual C-1 geranyl side chain,and hyperberin C(2)possesses a rare bicyclo[5.3.1]hendecane core.Taking compound 3 as a starting point,a plausible biosynthetic pathway to the bicyclic type B frameworks of 1 and 2 was proposed.

Ascyrones A-E, type B bicyclic ployprenylated acylphloroglucinol derivatives from Hypericum ascyron

Five new polycyclic polyprenylated acylphloroglucinols(1-5),ascyrones A-E,and four known compounds(6-9)were isolated from the aerial parts of Hypericum ascyron.All of the isolates containing a bicyclo[3.3.1]nonane-2,4,9-trione core and a benzoyl group,belonged to type B bicyclic polyprenylated acylphloroglucinols(BPAPs).Their structures and absolute configurations were established based on spectroscopic analyses and calculated electronic circular dichroism(ECD)data.The anti-inflammatory,neuroprotective and cytotoxicity activities of compounds 1-4 and 6-9 were evaluated.Compound 6 exhibited obvious anti-inflammatory activity in lipopolysaccharide(LPS)-induced RAW264.7 cells.Compounds 1 and 9 exhibited slight cytotoxicity against Hep3B cells.Meanwhile,compound 1 showed mild neuroprotective activity against corticosterone(CORT)-induced PC 12 cell damage at 10 μmol-L^(-1).

Polyprenylated acylphloroglucinols from the fruits of Hypericum henryi

Hyphenrones R–X(1–7), seven new polyprenylated acylphloroglucinols derivatives, were isolated from the fruits of Hypericum henryi, together with eight know analogues. Compounds 1 and 2 were elucidated to possess complex caged skeleton, while compounds 3–6 shared a common 3,9-epoxy moiety deriving from the normal polyprenylated acylphloroglucinols with a bicyclo[3.3.1]nonane-2,4,9-trione core. The new structures were elucidated on the basis of the interpretation of nuclear magnetic resonance(NMR) data, circular dichroism(CD) comparison, and single-crystal X-ray diffraction. In the bioassay, several compounds exhibited inhibitory activities against human tumor cell lines in vitro.

光学活性的α-甲基丁酰基间苯三酚类化合物绝对构型与旋光方向的关系及其合成

合成了14个新化合物,其中有12个是(S)-(+)-α-甲基丁酰基间苯三酚类化合物。通过对新化合物旋光资料的研究和分析,找到了它们绝对构型与旋光方向的关系。该规律在测定光学活性的α-甲基丁酰基间苯三酚类化合物的绝对构型和开发研究该类药物上,均具有一定的实际应用价值。

Diverse Polyphenols from Hypericum faberi

Six new polyphenols with diferent isoprenylated xanthones,isoprenylated acylphloroglucinols,and chromone architectures,hyperfaberols A-F(1-6),were isolated from the whole plants of Hypericum faberi along with seven other related known compounds.In which hyperfaberols A/B(1/2)and 12-13 were isoprenylated xanthones,hyperfaberols C-E(3-5)and 8-11 were seven isoprenylated acylphloroglucinol derivatives,while 6-7 were two chromones.Their structures were elucidated by comprehensive analysis of their spectroscopic data as well as detailed comparison with the literature data.Compounds 1 and 11 showed cytotoxities against the human esophageal cancer cell line(ECA-109)and the pancreatic tumor cell line(PANC-1)in vitro,respectively.

Antibacterial Activity of Acylglucinol Derivatives against Flavobacterium columnare

Columnaris (caused by Flavobacterium columnare) is one of the most common bacterial diseases affecting the pond-raised channel catfish (Ictalurus punctatus) in the southeastern United States of America resulting in annual losses of millions of dollars. As part of our continuing effort to discover environmentally benign compounds for the control of columnaris disease, acyl derivatives of phloroglucinol were synthesized and tested against F. columnare using a rapid bioassay. Among the analogs that were tested, diacyl analogs showed very high antibacterial activity against F. columnare in the laboratory bioassay. Diisovaleryl and diisobutyryl analogs were found to have the strongest activity against F. columnare (isolate ALM-00-173) based on 24-h 50% inhibitory concentration (IC50) and minimum inhibitory concentration (MIC). Diisovaleryl and diisobutyryl analogs had IC50 values 0.82 mg/L and 0.80 mg/L, respectively, whereas the drug control florfenicol had an IC50 value of 0.81 mg/L. Diisovaleryl and diisobutyryl analogs also had 24-h relative-to- drug-control IC50 values around 1.0 indicating activities similar to florfenicol, which is included in medicated feed and is one of the current management approach for columnaris.

木竹子枝叶的化学成分及细胞毒和抗炎活性研究

采用硅胶柱色谱和HPLC等分离方法,对木竹子Garcinia multiflora枝叶的化学成分进行分离纯化,依据理化性质及波谱数据分析进行结构鉴定,从中分离鉴定了10个单体化合物,分别为：sampsonione L（1）、hyperibone G（2）、garcicowin C（3）、isogarcinol（4）、garcinialone（5）、clovane-2,9-diol（6）、caryolane-1,9β-diol（7）、异茴芹灵（8）,1,2,4-苯三酚（9）和2-羟基-4,6-二甲氧基苯乙酮（10）。化合物1~3和6~10为首次从该植物中分离得到,其中1~2和5~9为首次从该属植物中分离得到。对分离得到的多环多异戊烯基间苯三酚类化合物（1~5）进行了细胞毒和抗炎活性筛选,结果显示化合物3~5具有较好的细胞毒和抗炎活性。

常用药材绵马贯众活性成分研究

目的:研究绵马贯众中活性成分间苯三酚衍生物类化合物。方法:采用缓冲硅胶层析法分离纯化化合物,根据理化性质及波谱数据鉴定化合物结构。结果:从绵马贯众根茎的乙酸乙酯萃取部位分离到9个间苯三酚衍生物类化合物,现报道已鉴定的前3个化合物。分别为白绵马素AA(Ⅰ),白绵马素AP(Ⅱ),白绵马素PP(Ⅲ)。结论:化合物Ⅱ、Ⅲ为首次从自然界分离得到单体,首次在该植物中发现。首次报道了化合物Ⅱ和化合物Ⅲ碳氢NMR数据、化合物Ⅰ的碳谱数据,并利用多种2DNMR技术对这3个化合物的NMR数据进行了归属。

糙枝金丝桃间苯三酚类成分的研究

对藤黄科金丝桃属植物糙枝金丝桃Hypericum scabrum地上部分的化学成分进行了研究。利用多种色谱技术从糙枝金丝桃乙醇提取物中分离得到了10个间苯三酚类成分,包括1个新化合物,命名为hyperibrin H(1);其他化合物被分别鉴定为hypermongone A(2)、hypermongone E(3)、hypermongone F(4)、hypermongone G(5)、hypermongone H(6)、sampsonione L(7)、garcinielliptone I(8)、propolone C(9)、garcinielliptone N(10)。化合物2~10均为首次从该植物中分离得到。化合物5和6在10μM浓度下对谷氨酸诱导的神经元损伤具有保护作用。

金丝李果实化学成分的研究

采用溶剂提取法、正反相硅胶柱、半制备高效液相等多种色谱技术对金丝李果实的化学成分进行了分离纯化,得到了一个新化合物和一个已知化合物,并根据理化性质和现代波谱技术进行了结构鉴定,分别鉴定为金丝李内酯甲(2)和7-epi-isogarcinol(1)。

Chemical Constituents from Hypericum beanii

Objective To study the chemical constituents from the aerial parts of Hypericum beani/. Methods Various chromatographic techniques were used to separate the constituents and their structures were elucidated on the basis of extensive spectroscopic interpretation. Results Fifteen compounds were isolated from the aerial parts of H. beanii. Their structures were identified as hyperbeanol E （1）, （E）-Iinalool-l-oic acid （2）, （4S,5R）-5-（4＇-methyl-3＇-pentenyl）-4-hydroxy-5-methyl- dihydrofuran-2-one （3）, benzoic acid （4）, 4-（3-O-3＂）-3＂-methylbutenyl-6-phenyl- pyran-2-one （5）, 4-hydroxy-4a,7-dimethoxy-4,4a-dihydrodibenzo-p-dioxJn-2（3H）- one （6）, isoimperatorin （7）, 2,3-dimethoxyxanthone （8）, 3,4-dihydroxy-2- methoxyxanthone （9）, osajaxanthone （10）, nigrolineaxanthone F （1 1）, hypercohone G （12）, betulinic acid （1 3）, oleanolic acid 3.13-caffeate （14）, and isoastilbin （1 5）. Conclusion Compound 1 is a new menthane monoterpene derivative which owns an extra lactone ring. Compounds 2-7 and 10-1 5 are isolated from genus Hypericum Linn. for the first time and the other compounds are first obtained from the plants in H. beanii.

金丝桃属植物中多环多异戊烯基间苯三酚类成分和生物活性的研究进展

金丝桃属植物在我国广大地区均有分布,主要集中在西南地区,我国约有55种8亚种,物种类型丰富。金丝桃属植物的主要化学成分为黄酮类、氧杂蒽酮类以及间苯三酚类化合物,而间苯三酚衍生物因其结构中具有多环和多种支链取代的特征结构,所以结构类型丰富多样,同时这类成分具有抗肿瘤、抗病毒、抗菌、抗炎等生物活性。该研究对从金丝桃属植物中分离的344个多环多异戊烯基间苯三酚类化合物进行分类归纳,为金丝桃属多环多异戊烯基间苯三酚类化合物的开发和利用提供科学依据。

大叶藤黄醇的全合成研究

多环多异戊烯基间苯三酚(PPAPs)类天然产物大叶藤黄醇(xanthochymol)具有良好的抗癌和抗菌活性,目前没有任何关于其全合成的研究报道.本研究以3,3-二甲基戊二酸为起始原料,通过一系列步骤制备线性链状底物,再应用串联Dieckmann缩合反应构建双环[3.3.1]壬烷-2,4,9-三酮核心骨架.此方法成功地以11步反应实现了消旋体大叶藤黄醇的全合成,以10%的总收率得到了目标产物.通过本研究得到大叶藤黄醇侧链的一对非对映异构体,在^(1)H NMR、^(13)C NMR谱图上明确了它们之间的区别,也对未来分离鉴定和区分其侧链结构异构体提供了参考数据.

纤枝金丝桃中的一个新的多环多异戊烯基间苯三酚衍生物

采用硅胶柱色谱、反相C18色谱柱色谱、Sephadex LH-20凝胶柱色谱、高效液相色谱及中压半制备液相色谱等分离技术对纤枝金丝桃中的化学成分进行分离纯化,通过MS、NMR等波谱数据结合理化性质鉴定化合物结构。从纤枝金丝桃80%乙醇提取物中分离得到11个化合物,分别鉴定为hyperlagarone A(1)、hyperpatulone E(2)、hyperbeanol G(3)、uralione D(4)、tomoeone F(5)、pyramidatone A(6)、tomoeone A(7)、tomoeone B(8)、hyperbeanol C(9)、hyperbeanol A(10)、hypercohone G(11)。其中化合物1是未见报道的新化合物,化合物2~11是首次从该植物中分离得到。对11个化合物进行基于L6骨骼细胞的促葡萄糖摄取实验,结果显示化合物7、8均显示较强的促葡萄糖摄取活性。