Penicine A(1),a meroterpenoid featuring a novel 3/5/6/6/11/6/6 polycyclic backbone,together with two new metabolites,penicines B(2)and C(4),and six known compounds,were isolated from the mangrove rhizosphere soil-deri...Penicine A(1),a meroterpenoid featuring a novel 3/5/6/6/11/6/6 polycyclic backbone,together with two new metabolites,penicines B(2)and C(4),and six known compounds,were isolated from the mangrove rhizosphere soil-derived fungus Penicillium brefeldianum SMU03.The structures of these metabolites were elucidated through extensive spectroscopic analysis combined with quantum chemical calculations.Notably,1 exhibits a highly unusual molecular architecture,incorporating a dioxaspiro[4.5]decane motif and a rare bridgehead double bond(anti-Bredt system).A plausible biosynthetic pathway,involving sequential intermolecular[4+2]cycloaddition reactions,is proposed.Additionally,meroterpenoids 1 and 3 demonstrate significant antifibrotic activity in transforming growth factorβ1(TGF-β1)-induced human renal proximal tubular epithelial cells.展开更多
The first total synthesis of marine sesquiterpene(hydro)quinone meroterpenoids dysideanones A and E–G(1 and 4–6)has been accomplished in an enantioselective and divergent way.The sesquiterpene fragment and the aroma...The first total synthesis of marine sesquiterpene(hydro)quinone meroterpenoids dysideanones A and E–G(1 and 4–6)has been accomplished in an enantioselective and divergent way.The sesquiterpene fragment and the aromatic moiety were efficiently connected via a site-selective and diastereoselective intermolecular alkylation of Wieland–Miescher ketone derivative 9 and benzyl bromide 10.The core 6/6/6/6-fused backbone of dysideanones was efficiently constructed through an intramolecular radical cyclization reaction.Dysideanone G(6)was easily prepared on a gram-scale and dysideanones A,E,and F(1,4,and 5)were divergently transformed from dysideanone G(6)in one or two steps.展开更多
Meroterpenoids are hybrid natural products that partially originate from the terpenoid pathway.Ganoderma meroterpenoids(GMs)are a type of meroterpenoids containing a 1,2,4-trisubstituted phenyl and a polyunsaturated t...Meroterpenoids are hybrid natural products that partially originate from the terpenoid pathway.Ganoderma meroterpenoids(GMs)are a type of meroterpenoids containing a 1,2,4-trisubstituted phenyl and a polyunsaturated terpenoid part.Over last 5 years,great efforts have been made to conduct phytochemistry research on the genus Ganoderma,which have led to the isolation and identification of a number of GMs.These newly reported GMs showed diverse structures and a wide range of biological activities.This review gives an overview of new GMs from genus Ganoderma and their biological activities and biosynthetic pathway,focusing on the period from 2013 until 2018.展开更多
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(...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.展开更多
Arnequinol A(1),featuring an unprecedented 6/6/3 tricyclic carbon skeleton fused with a heptatomic oxo-bridge,together with arnequinone A(2)bearing a highly conjugated methyl-shifting benzogeijerene skeleton,were isol...Arnequinol A(1),featuring an unprecedented 6/6/3 tricyclic carbon skeleton fused with a heptatomic oxo-bridge,together with arnequinone A(2)bearing a highly conjugated methyl-shifting benzogeijerene skeleton,were isolated from Arnebia euchroma.Their structures were elucidated by extensive spectro-scopic methods and quantum chemical calculations of the 13 C nuclear magnetic resonance(NMR)data and electronic circular dichroism(ECD)spectra.The plausible biosynthetic pathways for 1 and 2 were presented.In in vitro test,compound 2 showed potent neuroprotective activity against serum-deprivation induced PC12 cell damage at a concentration of 10μmol/L.展开更多
Hyperinoids A(1)and B(2),two prenylated acylphloroglucinol related meroterpenoids,were isolated from Hypericum patulum.Compound 1 incorporates an unprecedented 11,12-dioxatetracyclo[5.4.3.01,7.04,14]tetradecane system...Hyperinoids A(1)and B(2),two prenylated acylphloroglucinol related meroterpenoids,were isolated from Hypericum patulum.Compound 1 incorporates an unprecedented 11,12-dioxatetracyclo[5.4.3.01,7.04,14]tetradecane system,while 2 possesses a unique 10,11-dioxatetracyclo[5.3.3.01,7.04,13]tridecane syste m.Their structures were established by spectro scopic analysis and X-ray crystallographic data.Compounds 1 and 2 were identified as potent NF-κB inhibitors and suppressed the LPS-induced inflammatory responses in RAW 246.7 macrophages and primary mouse BMDM cells.展开更多
Three sesquiterpene-based meroterpenoids psiguamers A-C(1-3)with new skeletons were isolated from Psidium guajava leaves.Compounds(±)-1 and(±)-2 were two pairs of humulene-de「ived meroterpenoids bearing a r...Three sesquiterpene-based meroterpenoids psiguamers A-C(1-3)with new skeletons were isolated from Psidium guajava leaves.Compounds(±)-1 and(±)-2 were two pairs of humulene-de「ived meroterpenoids bearing a rare methylated benzoylphloroglucinol unit,while 3 was an unprecedented adduct of bicyclogermacrene and methylated benzoylphloroglucinol.Their structures were determined based on comprehensive analyses of spectroscopic data,calculated electronic circular dichroism(ECD)spectra,total synthesis,and X-ray crystallographic data.The biomimetic synthesis of(±)-1 and(±)-2 was achieved.Compound(+)-1 exhibited cytotoxic activities against five human tumor cell lines(HCT-116,HepG2,BGC-823,A549,and U251),with IC_(50) values of 2.94,9.01,6.45,5.42,and 5.33 μmol/L,respectively.展开更多
Phytochemical investigation of the MeOH extract of twigs and leaves of Baeckea frutescens led to the isolation of seven new polymethylated phloroglucinol meroterpenoids(PPMs),named baeckfrutones M-S(1-7).Their structu...Phytochemical investigation of the MeOH extract of twigs and leaves of Baeckea frutescens led to the isolation of seven new polymethylated phloroglucinol meroterpenoids(PPMs),named baeckfrutones M-S(1-7).Their structures and absolute configurations were determined by spectroscopic analyses,chiral-phase HPLC analysis,and electronic circular dichroism(ECD)calculations.PPM 1 is a novel meroterpenoid possessing a 6/6/5/3 tetracyclic skeleton in PPMs,whereas 3 and 4 are the first hydroxytasmanone type phloroglucinol-monoterpene hybrids.(+)-2 and 7 displayed potent antiinflammatory activity with IC50 values of 20.86±0.60 and 36.21±1.18 lL,respectively.展开更多
Periconones B-E（1-4）,four new polyketide-terpenoid hybrid molecules were isolated from the endophytic fungus Periconia sp.F-31.Their structures and absolute configurations were established by extensive spectroscopic...Periconones B-E（1-4）,four new polyketide-terpenoid hybrid molecules were isolated from the endophytic fungus Periconia sp.F-31.Their structures and absolute configurations were established by extensive spectroscopic data analysis and electronic circular dichroism（ECD）.Compound 4 exhibited in vitro cytotoxic activity against the human MCF-7 tumor cell line with an IC_（50） value of 4.2 μmol/L,and compound 1 displayed anti-HIV activity with an IC_（50） value of 18.0 μmol/L.展开更多
Guajadials C-F(1-4),four sesquiterpenoid-based meroterpenoids with unprecedented skeletons were isolated from the leaves of Psidium guajava.Their structures and relative configurations were established by extensive sp...Guajadials C-F(1-4),four sesquiterpenoid-based meroterpenoids with unprecedented skeletons were isolated from the leaves of Psidium guajava.Their structures and relative configurations were established by extensive spectroscopic analysis.A possible biosynthetic pathway for 1-4 was also proposed.展开更多
Under the guidance of the approach which integrates molecular networking,MolNetEnhancer and Net-work Annotation Propagation(NAP),daphnaltaicanoids A and B(1 and 2)with unprecedented 9-oxa-tetracyclo[6.6.1.0^(2,6).0^(8...Under the guidance of the approach which integrates molecular networking,MolNetEnhancer and Net-work Annotation Propagation(NAP),daphnaltaicanoids A and B(1 and 2)with unprecedented 9-oxa-tetracyclo[6.6.1.0^(2,6).0^(8,13)]pentadecane and tetracyclo[5.3.0.1^(2,5).2^(4,11)]tridecane central frameworks were iso-lated from Daphne altaica Pall.,representing two types of unparalleled meroterpenoid cores.Their struc-tures were elucidated by extensive spectroscopic analysis,nuclear magnetic resonance(NMR)calcula-tions,DP4+analysis and electronic circular dichroism(ECD)calculations.The plausible biosynthetic path-ways for 1 and 2 were postulated.Biologically,2 exerted potent neuroprotective activities which were su-perior to trolox at 12.5 and 25μmol/L.Moreover,1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil.Molecular docking simulations were performed to explore the inter-molecular interaction of compounds 1 and 2 with acetylcholinesterase.The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.展开更多
Here,we report a concise and divergent enantioselective total synthesis of marine sesquiterpene quinone meroterpenoids(+)-dysidavarones A–C(1–3)using predysidavarone 6 as a key common intermediate.The highly straine...Here,we report a concise and divergent enantioselective total synthesis of marine sesquiterpene quinone meroterpenoids(+)-dysidavarones A–C(1–3)using predysidavarone 6 as a key common intermediate.The highly strained and bridged eight-membered carbocycle of predysidavarone 6 was constructed by a one-pot intermolecular alkylation and intramolecular arylation of Wieland–Miescher ketone derivative 11 and benzyl bromide 12.The total synthesis of(+)-dysidavarones A–C(1–3)was achieved from predysidavarone 6 in a divergent manner by a late-stage introduction of the ethoxy group,which reveals the possible source of the ethoxy group within(+)-dysidavarones A–C(1–3)and provides a late-stage modifiable route for the synthesis of dysidavarone analogs for further anti-cancer activity evaluation.展开更多
Amphichoterpenoids A-C(1-3),unprecedented picoline-derived meroterpenoids possessing a pyrano[3,2-c]pyridinyl-g-pyranone scaffold,were characterized from the ascidian-derived fungus Amphichorda felina SYSU-MS7908.Thei...Amphichoterpenoids A-C(1-3),unprecedented picoline-derived meroterpenoids possessing a pyrano[3,2-c]pyridinyl-g-pyranone scaffold,were characterized from the ascidian-derived fungus Amphichorda felina SYSU-MS7908.Their structures were elucidated by spectroscopic methods,X-ray diffraction and electronic circular dichroism(ECD)calculations.A plausible biosynthetic pathway was proposed.The isolated compounds displayed moderate inhibitory activity against acetylcholinesterase with 50%inhibiting concentration(IC_(50))values of 18.8-53.2 mmol/L.展开更多
Phytochemical investigation of the aerial parts of Baeckea frutescens resulted in the isolation of three new mono-or sesquiterpene-based meroterpenoids, frutescones S-U(1-3), and one pair of new(±)-5,7-dihydroxy-...Phytochemical investigation of the aerial parts of Baeckea frutescens resulted in the isolation of three new mono-or sesquiterpene-based meroterpenoids, frutescones S-U(1-3), and one pair of new(±)-5,7-dihydroxy-8-isobutyryl-6-methyldihydroflavonol(4). Their structures and absolute configurations were established by HR-ESI-MS, 1D and 2D NMR, and quantum chemical ECD calculation. Compound 1 exhibited inhibitory effect on NO production in LPS-activated RAW 264.7 macrophages with an IC50 value being 0.81 μmol·L–1.展开更多
Five pairs of optically pure meroterpenoid enantiomers(1 a/1 b-5 a/5 b)and two known compounds(6 and 7)were isolated from Rhododendron fastigiatum.Compounds 1 a/1 b-5 a/5 b were resolved from naturally scalemic mixtur...Five pairs of optically pure meroterpenoid enantiomers(1 a/1 b-5 a/5 b)and two known compounds(6 and 7)were isolated from Rhododendron fastigiatum.Compounds 1 a/1 b-5 a/5 b were resolved from naturally scalemic mixtures by chiral HPLC.Their structures were elucidated by spectroscopic methods,X-ray crystallographic experiments,and ECD analyses.Compounds 1 a/1 b,2 a/2 b,3 b,4 a/4 b,and 5 a/5 b were new meroterpenoids with different polycyclic systems.Two enantiomeric pairs(2 a/2 b and 3 a/3 b),6,and 7 exhibited inhibitory effects on protein tyrosine phosphatase 1 B(PTP1 B)in vitro.展开更多
Terpenoids with quinoid structures are found as natural products. This includes steroidal quinones, quinones with a secosteroid structure and meroterpenoid quinones. Importantly, catechol estrogens as endogenous metab...Terpenoids with quinoid structures are found as natural products. This includes steroidal quinones, quinones with a secosteroid structure and meroterpenoid quinones. Importantly, catechol estrogens as endogenous metabolites of estradiol and estrone are precursors of reactive quinones and semiquinones, which are thought to contribute to estrogen-induced carcinogenesis. On the other hand, a number of quinones that include substituted naphthoquinones and anthraquinones are highly cytotoxic and have been used in cancer treatment. This makes the structures interesting synthetic targets. The following is a review of important natural and synthetic terpenoid and steroid quinone hybrids.展开更多
Meroterpenoids are secondary metabolites partially derived from the terpenoid biosynthetic pathway,and are widely distributed in plants,animals,and fungi.These natural products possess complex backbone structures and ...Meroterpenoids are secondary metabolites partially derived from the terpenoid biosynthetic pathway,and are widely distributed in plants,animals,and fungi.These natural products possess complex backbone structures and diverse bioactivities.Ganoderma meroterpenoids(GMs)form a distinct group of meroterpenoids were characterized by the presence of 1,2,4-trisubstituted phenyl and polyunsaturated terpene moieties.Various Ganoderma species have been extensively studied,leading to the discovery of several structurally unique meroterpenoids with significant pharmacological activities.After the first isolation and identification of GMs in 2000,over 300 compounds from 14 species have been characterized for their structures and biological activities.The structures and activities of some GMs from different Ganoderma species vary greatly,probably due to significant differences in the genome and transcriptome of different Ganoderma species.We predicted the related enzymes based on the reported Ganoderma genome and proposed the biosynthetic pathway related to GMs.The results presented in this review provide a scientific foundation for the comprehensive exploration and utilization of diverse Ganoderma resources.展开更多
Eight new polycyclic phloroglucinol meroterpenoids guajamers A-H(1-8),a methylated benzoylphloroglucinol meroterpenoid guajamer I(9)representing a new skeleton,and two known analogues(10 and 11)were isolated from the ...Eight new polycyclic phloroglucinol meroterpenoids guajamers A-H(1-8),a methylated benzoylphloroglucinol meroterpenoid guajamer I(9)representing a new skeleton,and two known analogues(10 and 11)were isolated from the leaves of Psidium guajava.The structures of new molecules were elucidated by detailed analysis of spectroscopic data,and those of 1,2,8,and 9 were unambiguously confirmed by single-crystal X-ray diffraction study.Structurally,compounds 1-8 were sesquiterpene and monoterpene-based meroterpenoids with rearranged skeletons,while compound 9 was the first case of 3-alkyl-5-formyl-benzoylphloroglucinol-coupled sesquiterpene containing an unusual C-l-spiro-fused 6/6/9/4 polycyclic skeleton.In addition,all the isolated compounds were evaluated for their antibacterial activity against three bacterial strains,and most of them(compounds 2-7,10,and 11)showed antibacterial activity against Staphylococcus aureus and Staphylococcus epidermidis with MIC values of 8-32 μmol/L.These findings suggested that meroterpenoids isolated from Psidium guajava can be considered as potential antibacterial leading compounds for pharmaceutical industry.展开更多
Psidium guajava Linn.(family Myrtaceae),is commonly known as guava.Guava is consumed in large quantities throughout the world due to its ease of cultivation and high nutritional value.As an important perennial fruit t...Psidium guajava Linn.(family Myrtaceae),is commonly known as guava.Guava is consumed in large quantities throughout the world due to its ease of cultivation and high nutritional value.As an important perennial fruit tree distributed around the world,guava has been widely used to manage various diseases in traditional medicine.Guava has been shown significant bioactivity such as antioxidant,anti-inflammatory,immunomodulatory,antimicrobial,antidiabetic,and anticancer properties.A large number of studies indicated that guava contains various type of phytochemicals including monoterpenes,sesquiterpenes,triterpenes,phenolics,and meroterpenoids.Among them,meroterpenoids are characteristic components of guava,which are hybrid of acylphloroglucinol with terpenoids(monoterpenes,sesquiterpenes).Modern pharmacological investigations showed intricate Psidium meroterpenoids possess a wide range of bioactivities.Although a large and growing body of literatures have investigated the Psidium meroterpenoids isolated from guava,a comprehensive review of Psidium meroterpenoids and their bioactivities has not been conducted.Therefore,this review provides a comprehensive compile of 75 meroterpenoids isolated from guava and their bioactivities between 2007 and May 2022.Furthermore,the possible biosynthesis way and future directions of Psidium meroterpenoids have also been discussed.展开更多
Hyperlanins A(1)and B(2),two highly rearranged polycyclic polyprenylated acylphloroglucinol(PPAP)-related meroterpenoids based on different new carbon skeletons,were isolated from Hypericum lancasteri.Compound 1 incor...Hyperlanins A(1)and B(2),two highly rearranged polycyclic polyprenylated acylphloroglucinol(PPAP)-related meroterpenoids based on different new carbon skeletons,were isolated from Hypericum lancasteri.Compound 1 incorporates an unprecedented 5/6/7/5 ring system featuring a 3,13-dioxatetracyclo[9.2.1.12.5.01.8]pentadecane core.Compound 2 possesses a unique compact 6/6/5/6/6/5/6 ring system with a caged tetracyclo[6.2.1.13.8.05,11]dodecane motif.Their structures were established by spectroscopic data,X-ray diffraction,and computational approaches.Both compounds showed anti-inflammatory activity in vitro.Compounds 1 and 2 could decrease the lipopolysaccharide(LPS)-/nigericin-induced IL-1βrelease in THP-1 cells.Both compounds also showed inhibition in hypoxia-inducible factor-1α(HIF-1αa)pathway luciferase reporter assay.展开更多
基金supported by the National Natural Science Foundation of China(Nos.82104039 and 82404471)Guangdong Science Foundation for Young Top-Notch Talent of Zhu-Jiang Talent Plan(No.0920220225)+1 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2023B1515120053 and 2022A1515111026)Guangzhou Municipal Science and Technology Bureau Foundation(No.2024A04J2704).
文摘Penicine A(1),a meroterpenoid featuring a novel 3/5/6/6/11/6/6 polycyclic backbone,together with two new metabolites,penicines B(2)and C(4),and six known compounds,were isolated from the mangrove rhizosphere soil-derived fungus Penicillium brefeldianum SMU03.The structures of these metabolites were elucidated through extensive spectroscopic analysis combined with quantum chemical calculations.Notably,1 exhibits a highly unusual molecular architecture,incorporating a dioxaspiro[4.5]decane motif and a rare bridgehead double bond(anti-Bredt system).A plausible biosynthetic pathway,involving sequential intermolecular[4+2]cycloaddition reactions,is proposed.Additionally,meroterpenoids 1 and 3 demonstrate significant antifibrotic activity in transforming growth factorβ1(TGF-β1)-induced human renal proximal tubular epithelial cells.
基金Financial support for this work was provided by the National Natural Science Foundation of China(Nos.22171146,21971121,and 22188101)the Fundamental Research Funds for the Central Universities,Nankai University(No.63231199)the State Key Laboratory of Medicinal Chemical Biology。
文摘The first total synthesis of marine sesquiterpene(hydro)quinone meroterpenoids dysideanones A and E–G(1 and 4–6)has been accomplished in an enantioselective and divergent way.The sesquiterpene fragment and the aromatic moiety were efficiently connected via a site-selective and diastereoselective intermolecular alkylation of Wieland–Miescher ketone derivative 9 and benzyl bromide 10.The core 6/6/6/6-fused backbone of dysideanones was efficiently constructed through an intramolecular radical cyclization reaction.Dysideanone G(6)was easily prepared on a gram-scale and dysideanones A,E,and F(1,4,and 5)were divergently transformed from dysideanone G(6)in one or two steps.
基金supported by the National Natural Science Foundation of China(No.21702209 and No.81172940)Foundation of State Key Laboratory of Phytochemistry and Plant Resources in West China(P2010-ZZ14).
文摘Meroterpenoids are hybrid natural products that partially originate from the terpenoid pathway.Ganoderma meroterpenoids(GMs)are a type of meroterpenoids containing a 1,2,4-trisubstituted phenyl and a polyunsaturated terpenoid part.Over last 5 years,great efforts have been made to conduct phytochemistry research on the genus Ganoderma,which have led to the isolation and identification of a number of GMs.These newly reported GMs showed diverse structures and a wide range of biological activities.This review gives an overview of new GMs from genus Ganoderma and their biological activities and biosynthetic pathway,focusing on the period from 2013 until 2018.
基金financially supported by Projects of International Cooperation and Exchanges NSFC(NSFC-VR,No.81361138020)National Science and Technology Major Projects for"Major New Drugs Innovation and Development",Research and Development of New Drug Varieties from Natural Product Sources and Their Key Innovative Technological Systems(Nos.2018ZX09711001-001-001 and 2018ZX09711001-001-003)the CAMS Innovation Fund for Medical Sciences(CIFMS),the CAMS Initiative for Innovative Medicine(CAMS-I2M,No.2016-I2M-1-010)。
文摘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.
基金supported by the CAMS Innovation Fund for Medical Sciences(No.2016-I2M-1-010,China).
文摘Arnequinol A(1),featuring an unprecedented 6/6/3 tricyclic carbon skeleton fused with a heptatomic oxo-bridge,together with arnequinone A(2)bearing a highly conjugated methyl-shifting benzogeijerene skeleton,were isolated from Arnebia euchroma.Their structures were elucidated by extensive spectro-scopic methods and quantum chemical calculations of the 13 C nuclear magnetic resonance(NMR)data and electronic circular dichroism(ECD)spectra.The plausible biosynthetic pathways for 1 and 2 were presented.In in vitro test,compound 2 showed potent neuroprotective activity against serum-deprivation induced PC12 cell damage at a concentration of 10μmol/L.
基金financially supported by Fudan-SIMM Joint Research Fund(No.FU-SIMM20181011)。
文摘Hyperinoids A(1)and B(2),two prenylated acylphloroglucinol related meroterpenoids,were isolated from Hypericum patulum.Compound 1 incorporates an unprecedented 11,12-dioxatetracyclo[5.4.3.01,7.04,14]tetradecane system,while 2 possesses a unique 10,11-dioxatetracyclo[5.3.3.01,7.04,13]tridecane syste m.Their structures were established by spectro scopic analysis and X-ray crystallographic data.Compounds 1 and 2 were identified as potent NF-κB inhibitors and suppressed the LPS-induced inflammatory responses in RAW 246.7 macrophages and primary mouse BMDM cells.
基金This work was supported by the National Natural Science Foundation of China(No.21772234)the National New Drug Innovation Major Project of China(Nos.2018ZX09735006 and 2018ZX09711001-002-010)+1 种基金CAMS Innovation Fund for Medical Sciences(Nos.2016-I2M-2-003 and 2017-I2M-3-010)the independent project of State Key Laboratory of Bioactive Substance and Function of Natural Medicines(No.GTZA201803).
文摘Three sesquiterpene-based meroterpenoids psiguamers A-C(1-3)with new skeletons were isolated from Psidium guajava leaves.Compounds(±)-1 and(±)-2 were two pairs of humulene-de「ived meroterpenoids bearing a rare methylated benzoylphloroglucinol unit,while 3 was an unprecedented adduct of bicyclogermacrene and methylated benzoylphloroglucinol.Their structures were determined based on comprehensive analyses of spectroscopic data,calculated electronic circular dichroism(ECD)spectra,total synthesis,and X-ray crystallographic data.The biomimetic synthesis of(±)-1 and(±)-2 was achieved.Compound(+)-1 exhibited cytotoxic activities against five human tumor cell lines(HCT-116,HepG2,BGC-823,A549,and U251),with IC_(50) values of 2.94,9.01,6.45,5.42,and 5.33 μmol/L,respectively.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.31570363 and 31770391)Key Research and Development Plan of Yunnan Province–Special Project of Science and Technology in Yunnan Province(2017IB007)+2 种基金Major Biomedical Project of Yunnan Province(2018ZF005)Innovation Team of the Ministry of Education(No.IRT-17R49)the Foundation of State Key Laboratory of Phytochemistry and Plant Resources in West China(P2017-ZZ04 and P2017-KF06),Kunming Institute of Botany,Chinese Academy of Sciences.
文摘Phytochemical investigation of the MeOH extract of twigs and leaves of Baeckea frutescens led to the isolation of seven new polymethylated phloroglucinol meroterpenoids(PPMs),named baeckfrutones M-S(1-7).Their structures and absolute configurations were determined by spectroscopic analyses,chiral-phase HPLC analysis,and electronic circular dichroism(ECD)calculations.PPM 1 is a novel meroterpenoid possessing a 6/6/5/3 tetracyclic skeleton in PPMs,whereas 3 and 4 are the first hydroxytasmanone type phloroglucinol-monoterpene hybrids.(+)-2 and 7 displayed potent antiinflammatory activity with IC50 values of 20.86±0.60 and 36.21±1.18 lL,respectively.
文摘Periconones B-E（1-4）,four new polyketide-terpenoid hybrid molecules were isolated from the endophytic fungus Periconia sp.F-31.Their structures and absolute configurations were established by extensive spectroscopic data analysis and electronic circular dichroism（ECD）.Compound 4 exhibited in vitro cytotoxic activity against the human MCF-7 tumor cell line with an IC_（50） value of 4.2 μmol/L,and compound 1 displayed anti-HIV activity with an IC_（50） value of 18.0 μmol/L.
基金The authors acknowledge the National Basic Research Program of China(973 Program,2009CB522300)the“West Light”program of Chinese Academy of Sciences,and the National Natural Science Foundation of China(U1132607).
文摘Guajadials C-F(1-4),four sesquiterpenoid-based meroterpenoids with unprecedented skeletons were isolated from the leaves of Psidium guajava.Their structures and relative configurations were established by extensive spectroscopic analysis.A possible biosynthetic pathway for 1-4 was also proposed.
基金supported by the National Natural Science Foundation of China(Nos.82073736,81872766)Science and Technology Planning Project of Liaoning Province(No.2021JH1/10400049)Liaoning revitalization talents program(Nos.XLYC2002066,XLYC2007180).
文摘Under the guidance of the approach which integrates molecular networking,MolNetEnhancer and Net-work Annotation Propagation(NAP),daphnaltaicanoids A and B(1 and 2)with unprecedented 9-oxa-tetracyclo[6.6.1.0^(2,6).0^(8,13)]pentadecane and tetracyclo[5.3.0.1^(2,5).2^(4,11)]tridecane central frameworks were iso-lated from Daphne altaica Pall.,representing two types of unparalleled meroterpenoid cores.Their struc-tures were elucidated by extensive spectroscopic analysis,nuclear magnetic resonance(NMR)calcula-tions,DP4+analysis and electronic circular dichroism(ECD)calculations.The plausible biosynthetic path-ways for 1 and 2 were postulated.Biologically,2 exerted potent neuroprotective activities which were su-perior to trolox at 12.5 and 25μmol/L.Moreover,1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil.Molecular docking simulations were performed to explore the inter-molecular interaction of compounds 1 and 2 with acetylcholinesterase.The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.
基金financially supported by the National Natural Science Foundation of China(Nos.22171146,21971121,and 22188101 to ZL)the China Postdoctoral Science Foundation(No.2021M701775 to CC)。
文摘Here,we report a concise and divergent enantioselective total synthesis of marine sesquiterpene quinone meroterpenoids(+)-dysidavarones A–C(1–3)using predysidavarone 6 as a key common intermediate.The highly strained and bridged eight-membered carbocycle of predysidavarone 6 was constructed by a one-pot intermolecular alkylation and intramolecular arylation of Wieland–Miescher ketone derivative 11 and benzyl bromide 12.The total synthesis of(+)-dysidavarones A–C(1–3)was achieved from predysidavarone 6 in a divergent manner by a late-stage introduction of the ethoxy group,which reveals the possible source of the ethoxy group within(+)-dysidavarones A–C(1–3)and provides a late-stage modifiable route for the synthesis of dysidavarone analogs for further anti-cancer activity evaluation.
基金the National Natural Science Foundation of China(No.41806155)the Guangdong MEPP Fund(No.GDOE(2019)A21)+2 种基金the National Key R&D Program of China(No.2019YFC0312501)the Natural Science Foundation of Guangdong Province(No.2018A030310304)the Key-Area Research and Development Program of Guangdong Province(No.2020B1111030005)for generous support。
文摘Amphichoterpenoids A-C(1-3),unprecedented picoline-derived meroterpenoids possessing a pyrano[3,2-c]pyridinyl-g-pyranone scaffold,were characterized from the ascidian-derived fungus Amphichorda felina SYSU-MS7908.Their structures were elucidated by spectroscopic methods,X-ray diffraction and electronic circular dichroism(ECD)calculations.A plausible biosynthetic pathway was proposed.The isolated compounds displayed moderate inhibitory activity against acetylcholinesterase with 50%inhibiting concentration(IC_(50))values of 18.8-53.2 mmol/L.
基金the National Natural Science Foundation of China (Nos.81803392, 81573309 and 81973206)the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No. 2017BT01Y036)+3 种基金the National Key R&D Program of China (No. 2017YFC1703802)theNatural Science Foundation of Jiangsu Province (No. BK20180566)the Funding of Double First-rate Discipline Innovation Team (Nos.CPU2018GF05 and CPU2018GY11)the China Postdoctoral Science Foundation funded project (No. 2018M630644)。
文摘Phytochemical investigation of the aerial parts of Baeckea frutescens resulted in the isolation of three new mono-or sesquiterpene-based meroterpenoids, frutescones S-U(1-3), and one pair of new(±)-5,7-dihydroxy-8-isobutyryl-6-methyldihydroflavonol(4). Their structures and absolute configurations were established by HR-ESI-MS, 1D and 2D NMR, and quantum chemical ECD calculation. Compound 1 exhibited inhibitory effect on NO production in LPS-activated RAW 264.7 macrophages with an IC50 value being 0.81 μmol·L–1.
基金supported by the National Natural Science Foundation of China(No.81222045)the Fudan-SIMM Joint Research Fund(No.FU-SIMM20181011)
文摘Five pairs of optically pure meroterpenoid enantiomers(1 a/1 b-5 a/5 b)and two known compounds(6 and 7)were isolated from Rhododendron fastigiatum.Compounds 1 a/1 b-5 a/5 b were resolved from naturally scalemic mixtures by chiral HPLC.Their structures were elucidated by spectroscopic methods,X-ray crystallographic experiments,and ECD analyses.Compounds 1 a/1 b,2 a/2 b,3 b,4 a/4 b,and 5 a/5 b were new meroterpenoids with different polycyclic systems.Two enantiomeric pairs(2 a/2 b and 3 a/3 b),6,and 7 exhibited inhibitory effects on protein tyrosine phosphatase 1 B(PTP1 B)in vitro.
文摘Terpenoids with quinoid structures are found as natural products. This includes steroidal quinones, quinones with a secosteroid structure and meroterpenoid quinones. Importantly, catechol estrogens as endogenous metabolites of estradiol and estrone are precursors of reactive quinones and semiquinones, which are thought to contribute to estrogen-induced carcinogenesis. On the other hand, a number of quinones that include substituted naphthoquinones and anthraquinones are highly cytotoxic and have been used in cancer treatment. This makes the structures interesting synthetic targets. The following is a review of important natural and synthetic terpenoid and steroid quinone hybrids.
基金funded by the National Natural Science Foundation of China(No.U22A20369,32370069 and 31800031)the Natural Science Foundation of Heilongjiang Province of China(No.LH2023C035).
文摘Meroterpenoids are secondary metabolites partially derived from the terpenoid biosynthetic pathway,and are widely distributed in plants,animals,and fungi.These natural products possess complex backbone structures and diverse bioactivities.Ganoderma meroterpenoids(GMs)form a distinct group of meroterpenoids were characterized by the presence of 1,2,4-trisubstituted phenyl and polyunsaturated terpene moieties.Various Ganoderma species have been extensively studied,leading to the discovery of several structurally unique meroterpenoids with significant pharmacological activities.After the first isolation and identification of GMs in 2000,over 300 compounds from 14 species have been characterized for their structures and biological activities.The structures and activities of some GMs from different Ganoderma species vary greatly,probably due to significant differences in the genome and transcriptome of different Ganoderma species.We predicted the related enzymes based on the reported Ganoderma genome and proposed the biosynthetic pathway related to GMs.The results presented in this review provide a scientific foundation for the comprehensive exploration and utilization of diverse Ganoderma resources.
基金the National Natural Science Foundation of China(No.21772234)the National New Drug Innovation Major Project of China(Nos.2018ZX09735006,2018ZX09711001-001,and 2018ZX09711001-002-010)the independent project of State Key Laboratory of Bioactive Substance and Function of Natural Medicines(No.GTZA201803).
文摘Eight new polycyclic phloroglucinol meroterpenoids guajamers A-H(1-8),a methylated benzoylphloroglucinol meroterpenoid guajamer I(9)representing a new skeleton,and two known analogues(10 and 11)were isolated from the leaves of Psidium guajava.The structures of new molecules were elucidated by detailed analysis of spectroscopic data,and those of 1,2,8,and 9 were unambiguously confirmed by single-crystal X-ray diffraction study.Structurally,compounds 1-8 were sesquiterpene and monoterpene-based meroterpenoids with rearranged skeletons,while compound 9 was the first case of 3-alkyl-5-formyl-benzoylphloroglucinol-coupled sesquiterpene containing an unusual C-l-spiro-fused 6/6/9/4 polycyclic skeleton.In addition,all the isolated compounds were evaluated for their antibacterial activity against three bacterial strains,and most of them(compounds 2-7,10,and 11)showed antibacterial activity against Staphylococcus aureus and Staphylococcus epidermidis with MIC values of 8-32 μmol/L.These findings suggested that meroterpenoids isolated from Psidium guajava can be considered as potential antibacterial leading compounds for pharmaceutical industry.
基金This work was financially supported by the National Natural Science Foundation of China(U1802287 and 32170408)the Ten Thousand Talents Plan of Yunnan Province for Industrial Technology Leading Talents(YNWR-CYJS-2019-011)+1 种基金the Project of Yunnan Characteristic Plant Screening and R&D Service CXO Platform(2022YKZY001)the State Key Laboratory of Phytochemistry and Plant Resources in West China(P2019-ZZ02).
文摘Psidium guajava Linn.(family Myrtaceae),is commonly known as guava.Guava is consumed in large quantities throughout the world due to its ease of cultivation and high nutritional value.As an important perennial fruit tree distributed around the world,guava has been widely used to manage various diseases in traditional medicine.Guava has been shown significant bioactivity such as antioxidant,anti-inflammatory,immunomodulatory,antimicrobial,antidiabetic,and anticancer properties.A large number of studies indicated that guava contains various type of phytochemicals including monoterpenes,sesquiterpenes,triterpenes,phenolics,and meroterpenoids.Among them,meroterpenoids are characteristic components of guava,which are hybrid of acylphloroglucinol with terpenoids(monoterpenes,sesquiterpenes).Modern pharmacological investigations showed intricate Psidium meroterpenoids possess a wide range of bioactivities.Although a large and growing body of literatures have investigated the Psidium meroterpenoids isolated from guava,a comprehensive review of Psidium meroterpenoids and their bioactivities has not been conducted.Therefore,this review provides a comprehensive compile of 75 meroterpenoids isolated from guava and their bioactivities between 2007 and May 2022.Furthermore,the possible biosynthesis way and future directions of Psidium meroterpenoids have also been discussed.
基金supports from the National Natural Science Foundation of China(Grant No.22277074)Zhiyuan Future Scholar Program(Grant No.ZIRC2022-14)of Zhiyuan College,Shanghai Jiao Tong University are gratefully acknowledged.
文摘Hyperlanins A(1)and B(2),two highly rearranged polycyclic polyprenylated acylphloroglucinol(PPAP)-related meroterpenoids based on different new carbon skeletons,were isolated from Hypericum lancasteri.Compound 1 incorporates an unprecedented 5/6/7/5 ring system featuring a 3,13-dioxatetracyclo[9.2.1.12.5.01.8]pentadecane core.Compound 2 possesses a unique compact 6/6/5/6/6/5/6 ring system with a caged tetracyclo[6.2.1.13.8.05,11]dodecane motif.Their structures were established by spectroscopic data,X-ray diffraction,and computational approaches.Both compounds showed anti-inflammatory activity in vitro.Compounds 1 and 2 could decrease the lipopolysaccharide(LPS)-/nigericin-induced IL-1βrelease in THP-1 cells.Both compounds also showed inhibition in hypoxia-inducible factor-1α(HIF-1αa)pathway luciferase reporter assay.
