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.

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.

Hyperterpenoids A and B:Two pairs of unprecedented 6/6/4/6/6 polycyclic cyclobutane meroterpenoids with potent neuroprotective and anti-inflammatory activities from Hypericum beanii

Hyperterpenoid A(1)and B(2),two pairs of enantiomers,with an unprecedented 6/6/4/6/6 polycyclic skeleton,along with one known compoud hypermonone A(3)were isolated from Hypericum beanii.The racemate(±)-1 and(±)-2 were successfully separated into the two optically pure enantiomers(ee>99%)using a preparative HPLC system.Their absolute configurations were elucidated by extensive spectroscopic analyses and single-crystal X-ray diffraction method.The related plausible biogenetic pathways were pre sented.Compound 1-3 showed significant neuroprotective activity and potential antiinflammatory activity.The result that(+)-2 and(-)-2 presented different anti-inflammatory properties,may lead us to new discovery of structure activity relationship between racemates,enantiomers,and diastereomers,as well as further research regarding the binding of drugs to target proteins.

Hyperbenzones A and B,two 1,2-seco and rearranged polycyclic polyprenylated acylphloroglucinols from Hypericum beanii

Two novel seco-polycyclic polyprenylated acylphloroglucinols(PPAPs),hyperbenzones A(1)and B(2),were isolated from the roots of Hypericum beanii,together with one known biosynthetic congener 3.Compound 1 incorporates a 6/5/5 ring system with an unprecedented spiro[bicyclo[3.3.0]octane-3,1'-cyclohexane]-2,2'-dione motif.The structures of 1 and 2 were determined by a combination of high resolution electrospray ionization mass spectroscopy(HRESIMS),nuclear magnetic resonance(NMR)spectroscopic analyses,gage-independent atomic orbital(GIAO)NMR chemical shift calculation with DP4+analyses,electronic circular dichroism(ECD)calculation,and X-ray diffraction analysis.A 1,2-seco retroClaisen rearrangement from a bicyclo[3.3.1]nonane PPAP precursor and following chemodivergent radical cascade cyclizations are proposed as the key steps in the biosynthetic pathway to yield compounds 1 and2.Biological investigations indicated that compounds 1 and 3 could decrease intracellular lipid accumulation in a palmitic acid-induced nonalcoholic steatohepatitis(NASH)cell model.

Hybeanones A and B,Two Highly Modified Polycyclic Polyprenylated Acylphloroglucinols from Hypericum beanii

Hybeanones A and B(1 and 2),two highly oxygenated and rearranged polycyclic polyprenylated acylphloroglucinols(PPAPs),were isolated from the aerial parts of Hypericum beanii.Their structures comprising absolute configurations were elucidated by spectroscopic analysis,single-crystal X-ray diffraction,and quantum chemical calculations.Compounds 1 and 2 are defined by a newly assembled cyclopentanone unit fused to a tricyclic γ-lactone unit via a ketone carbonyl.The breakage of C-1/C-2 linkage via retro-Claisen reaction,attack from C-1 to C-19,and Baeyer-Villiger oxidation at C-1/C-23 bond were presumed to be the key steps in the assembly of 1 and 2.The isolates 1 and 2 showed potential acetylcholinesterase(AchE)inhibitory activities,with IC50 values of 21.34±1.48 and 18.79±2.36μmol/L,respectively.

New secondary metabolites with cytotoxicity from fungus Penicillium roqueforti

Two novel compounds including a cyclohelminthol type polyketide(namely oxaleimide K,1)and a maleimide deriva-tive(namely peniroquefortine A,2),and a new natural product(namely 2-(acetylamino)-N-[(1E)-2-phenylethenyl]-acetamide,3),together with four known compounds(4-7),were isolated and identified from fungus Penicillium roqueforti,which was separated from the root soil of Hypericum beanii N.Robson collected from the Shennongjia For-estry District,Hubei Province.Their structures including absolute configurations were mainly established by the NMR spectroscopy analyses and single-crystal X-ray diffraction experiment.Compound 1 represents the second example of a cyclohelminthol type polyketide,which features a rare 6/6/5/5 tetracyclic system and a branched aliphatic chain containing a terminal olefin(oct-1-en-3-yl)moiety,and compound 2 possesses an unprecedented carbon skeleton that is uniquely defined by a maleimide moiety linked to the respective 4-methylene-2-(3-methylbut-2-en-1-yl)-phenol and para-substituted aromatic moieties via the carbon-carbon bonds.Remarkably,the absolute configuration of a cyclohelminthol type polyketide as exemplified by compound 1 is determined by the single-crystal diffraction analysis for the first time,highlighting an E-configuration for the linkage of a succinimide moiety and a tetrahydro-furan moiety for 1 rather than a Z-configuration as previously reported in the biosynthesis study,which gives a new insight into the structural elucidation of this category of polyketides.Additionally,compound 1 exhibited significant cytotoxic activity against multiple tumor cells,especially against the Farage and SU-DHL-2 cells(IC_(50)<20μM,48 h).Further mechanism study revealed that compound 1 significantly induced cell cycle arrest in Farage and SU-DHL-2 cells by causing abnormal ROS level and triggering oxidative stress.

6种金丝桃属植物叶中分泌结构的研究

目的 寻找金丝桃属中草本植物含金丝桃素而木本不含的形态学及组织化学依据 ,为该属植物资源的开发利用提供依据。方法 对金丝桃属中 6种植物叶片进行解剖学研究 ,观察透明材料 ,并进行组织化学实验和石蜡切片观察。研究分泌结构在各种植物叶片中的分布和结构。结果 存在分泌细胞团和分泌囊 (道 )两类形态结构特点不同的分泌结构 ,草本植物中两者都有 ,而木本植物中只有分泌囊 (道 )。金丝桃素储存于分泌细胞团内。结论 为金丝桃属中只有草本植物含金丝桃素提供了依据。

六种金丝桃属植物叶中分泌结构的研究

目的 寻找金丝桃属中 ,草本植物含金丝桃素而木本不含的形态学及组织化学依据 ,为该属植物资源的开发利用提供依据。方法 对金丝桃属中 6种植物叶片进行解剖学研究 :观察透明材料 ,组织化学实验和观察石蜡切片。研究分泌结构在各种植物叶片中的分布和结构特征。结果 存在分泌细胞团和分泌囊 (道 )二类形态结构特点不同的分泌结构 ,草本植物中两者都有 ,而木本植物中只有分泌囊 (道 )。金丝桃素储存于分泌细胞团内。结论 金丝桃属中 。