Huperzine V, a new Lycopodium alkaloid, was isolated from the whole plant of Huperzia serrata, and the absolute stereochemistry was determined by X-ray crystallographic analysis.
Huperzine W, a novel 14 carbons Lycopodium alkaloid, was isolated from the whole plant of Huperzia serrata, and its stucture was determined by spectroscopic analysis.
Plant alkaloids,renowned for their structural diversity and bioactivity,are prominent in both modern and traditional medicine[1].Unraveling the intricacies of plant alkaloid biosynthesis could pave the way for the dis...Plant alkaloids,renowned for their structural diversity and bioactivity,are prominent in both modern and traditional medicine[1].Unraveling the intricacies of plant alkaloid biosynthesis could pave the way for the discovery of new natural products and pathways.It may also shed light on the roles of existing pathways in host biology and provide valuable tools for metabolic engineering in plants and microbes[2].Unlike other major classes of plant natural products,such as terpenoids and polyketides,the formation of alkaloid scaffolds does not conform to a uniform chemical theme or depend on a singular enzyme class[3].A case in point is the Lycopodium alkaloids in the Lycopodiaceae family,where the enzymes responsible for their core scaffold construction remain unidentified[4].展开更多
Phlegmine A(1),a novel type of Lycopodium alkaloid with a unique skeleton,was isolated from the rare and endangered herbal medicinal plant,Phlegmariurus phlegmaria.Spectroscopic methods and X-ray diffraction analysis ...Phlegmine A(1),a novel type of Lycopodium alkaloid with a unique skeleton,was isolated from the rare and endangered herbal medicinal plant,Phlegmariurus phlegmaria.Spectroscopic methods and X-ray diffraction analysis were employed to unambiguously elucidate the structure of phlegmine A(1).Furthermore,we realized the asymmetric total synthesis of the natural product phlegmine A(1)in 18 linear steps from commercial ingredients,achieving a 1.3%overall yield.An intramolecular carbene cyclization,dimethyldioxirane(DMDO)enamine oxidation,and Stevens rearrangement were exploited to establish the sterically congested vicinal quaternary centers,and an epimerization/aldol condensation/deacetylation reaction was utilized for the rapid assembly of enone at the final step.During our semisynthesis attempts,a novel transformation was developed to constructα-aminoketone from enamine N-oxide.Moreover,the synthetic sample obtained from this work enabled the successful verification of phlegmine A(1)as a new type of highly selective acidsensing ion channel 1a(ASIC1a)inhibitor,which also exerted an in vivo analgesic effect,rendering it a promising lead compound.展开更多
Two rare lyconadin-type Lycopodium alkaloids,lyconadins G(1)and H(2),together with four known ones(3–6),were isolated from Lycopodium complanatum.The structures were determined on the basis of their spectroscopic ana...Two rare lyconadin-type Lycopodium alkaloids,lyconadins G(1)and H(2),together with four known ones(3–6),were isolated from Lycopodium complanatum.The structures were determined on the basis of their spectroscopic analyses,and the absolute configuration of 1 was established by an X-ray crystallographic analysis.It is the first time to establish the absolute configuration of lyconadin-type Lycopodium alkaloid by an X-ray diffraction experiment.In addition,these findings may provide more information for the biosynthesis of lyconadins.展开更多
Lycophytes and ferns are unique and charismatic members of many terrestrial ecosystems and occupy the pivotal position in land plant origin and evolution.The Chinese lycophytes and ferns flora,with approximately 2000 ...Lycophytes and ferns are unique and charismatic members of many terrestrial ecosystems and occupy the pivotal position in land plant origin and evolution.The Chinese lycophytes and ferns flora,with approximately 2000 species,contributes a substantial component to the global lycophytes and ferns diversity,with estimates of 12000 species.Among them,about 433 species are medicinally recorded and researches based on their phytochemical properties are important topics in natural medicines.This paper reviewed the research history and current status of chemical constituents and biological activities of lycophytes and ferns,which had highlighted the research progress of our group.展开更多
A novel Ci7N Lycopodium alkaloid(LA),lycoplanine B(1),containing an unusual formyl group,along with two new LAs,lycoplanines C(2)and D(3),were isolated from the whole plant of Lycopodium complanatum.Their structures w...A novel Ci7N Lycopodium alkaloid(LA),lycoplanine B(1),containing an unusual formyl group,along with two new LAs,lycoplanines C(2)and D(3),were isolated from the whole plant of Lycopodium complanatum.Their structures were elucidated by extensive NMR techniques,including 1D-and 2D-NMR experiments,as well as comparing their spectral data with those of the known analogues.A possible biogenetic pathway for 1 was also proposed.展开更多
Objectives： To elucidate how ethanol extract of L. serratum（ELS） could exert anti-migratory effects on glioma with the suppression of nuclear factor kappa B（NF-κB） downstream pathway. Methods： Cell viability of...Objectives： To elucidate how ethanol extract of L. serratum（ELS） could exert anti-migratory effects on glioma with the suppression of nuclear factor kappa B（NF-κB） downstream pathway. Methods： Cell viability of ELS on C6 glioma was detected by 3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay. Nitric oxide（NO） assay and 2＇,7＇-dichlorofluorescin diacetate（DCFH-DA） assay were applied to measure NO production and reactive oxygen species（ROS） generation on lipopolysaccharide（LPS）-induced C6 glioma cells. NF-κB, mitogen-activated protein kinase（MAPK）, inducible nictric oxide synthase（i NOS） and cyclooxygenase-2（COX-2） protein were determined by Western blot. Wound healing assay was used to investigate the inhibitory effect of ELS on fetal bovine serum（FBS）-induced migration and matrix metalloproteinase（MMP）-9 and-2 activity was examined by zymography. Results： ELS suppressed LPS-induced phosphorylation of extracellular signal-regulated kinase（ERK）, c-Jun N-terminal kinase（JNK）, and p38 through inhibiting the expression of chemokine CCL2（or monocyte chemoattractant protein-1, MCP-1）. In addition, ELS inhibited the expression of i NOS, COX-2, and the production of NO by LPS in C6 glioma cells. ELS also significantly decreased serum-induced migration of C6 glioma cells in scratch wound healing in a dose-dependent manner（P〈0.01）. The activity of MMP-9 and-2 were also significantly attenuated by ELS with LPS treatment（P〈0.01）. Conclusion： Our results suggest that downregulation of MMP-9 gene expression might be involved in the anti-migration effect of ELS against LPS-induced C6 glioma cells.展开更多
Three new lycopodine-type alkaloids,4a-hydroxyanhydrolycodoline(1),4a,6a-dihydroxyanhydrolycodoline(2),and 6-epi-8b-acetoxylycoclavine(3),and an artifact,lycoposerramine G nitrate(4),along with seventeen related known...Three new lycopodine-type alkaloids,4a-hydroxyanhydrolycodoline(1),4a,6a-dihydroxyanhydrolycodoline(2),and 6-epi-8b-acetoxylycoclavine(3),and an artifact,lycoposerramine G nitrate(4),along with seventeen related known compounds,were isolated from the club moss Lycopodium japonicum Thunb.ex Murray(Lycopodiaceae).Their structures were elucidated by extensive spectroscopic methods as well as X-ray analysis.Compounds 1–4 were evaluated for their acetylcholine esterase inhibitory activity.展开更多
Two novel hydroperoxylated Lycopodium alkaloids, 11alpha-hydroperoxyphlegmariurine B (1) and 7-hydroperoxyphlegmariurine B (2), along with a known compound, phlegmanurine B (3), were isolated from the total alkaloid f...Two novel hydroperoxylated Lycopodium alkaloids, 11alpha-hydroperoxyphlegmariurine B (1) and 7-hydroperoxyphlegmariurine B (2), along with a known compound, phlegmanurine B (3), were isolated from the total alkaloid fraction of the Chinese medicinal herb Huperzia serrata (Thunb.) Trev. Their structures and relative configurations were elucidated on the basis of spectroscopic analyses.展开更多
t Three new lycodine-type Lycopodium alkaloids,namely 1-methyllycodine(1),8a-hydroxy-15,16-dehydro-desN-methyl-a-obscurine(2),N-methyl-16-hydroxyhuperzine B(3),and one new natural lycodine-type Lycopodium alkaloid,N-...t Three new lycodine-type Lycopodium alkaloids,namely 1-methyllycodine(1),8a-hydroxy-15,16-dehydro-desN-methyl-a-obscurine(2),N-methyl-16-hydroxyhuperzine B(3),and one new natural lycodine-type Lycopodium alkaloid,N-methylhuperzine A(4),along with 11 known analogues(5–15),were isolated from the whole plants of club moss Huperzia serrata.The structures of 1–4 were elucidated on the basis of NMR spectroscopic and mass spectrometry data.Among them,compound 1 was the first lycodine-type alkaloid possessing a methyl group at C-1.In addition,the structure of 5 was confirmed by the single-crystal X-ray crystallography data and its^(13)C NMR was reported for the first time in current study.Compounds 1–5 were tested their BACE1 inhibitory activity.展开更多
文摘Huperzine V, a new Lycopodium alkaloid, was isolated from the whole plant of Huperzia serrata, and the absolute stereochemistry was determined by X-ray crystallographic analysis.
文摘Huperzine W, a novel 14 carbons Lycopodium alkaloid, was isolated from the whole plant of Huperzia serrata, and its stucture was determined by spectroscopic analysis.
文摘Plant alkaloids,renowned for their structural diversity and bioactivity,are prominent in both modern and traditional medicine[1].Unraveling the intricacies of plant alkaloid biosynthesis could pave the way for the discovery of new natural products and pathways.It may also shed light on the roles of existing pathways in host biology and provide valuable tools for metabolic engineering in plants and microbes[2].Unlike other major classes of plant natural products,such as terpenoids and polyketides,the formation of alkaloid scaffolds does not conform to a uniform chemical theme or depend on a singular enzyme class[3].A case in point is the Lycopodium alkaloids in the Lycopodiaceae family,where the enzymes responsible for their core scaffold construction remain unidentified[4].
基金the National Natural Science Foundation of China(NSFCgrant no.21837003)+2 种基金the Joint Foundation of NSFC-Yunnan Province(grant no.U1502223)the Yunnan Revitalization Talent Support Program“Young Talent”Project,NSFC(grant no.81903521)the Natural Science Foundation of Yunnan Province,China(grant no.202001AT070067).
文摘Phlegmine A(1),a novel type of Lycopodium alkaloid with a unique skeleton,was isolated from the rare and endangered herbal medicinal plant,Phlegmariurus phlegmaria.Spectroscopic methods and X-ray diffraction analysis were employed to unambiguously elucidate the structure of phlegmine A(1).Furthermore,we realized the asymmetric total synthesis of the natural product phlegmine A(1)in 18 linear steps from commercial ingredients,achieving a 1.3%overall yield.An intramolecular carbene cyclization,dimethyldioxirane(DMDO)enamine oxidation,and Stevens rearrangement were exploited to establish the sterically congested vicinal quaternary centers,and an epimerization/aldol condensation/deacetylation reaction was utilized for the rapid assembly of enone at the final step.During our semisynthesis attempts,a novel transformation was developed to constructα-aminoketone from enamine N-oxide.Moreover,the synthetic sample obtained from this work enabled the successful verification of phlegmine A(1)as a new type of highly selective acidsensing ion channel 1a(ASIC1a)inhibitor,which also exerted an in vivo analgesic effect,rendering it a promising lead compound.
基金This work was financially supported by the NSFC-Joint Foundation of Yunnan Province(No.U1502223)the National Natural Science Foundation of China(No.21402212)+1 种基金the Science and Technology Program of Yunnan Province(No.2015FB173)the CAS“Light of West China”Program and Youth Innovation Promotion Association CAS(X.-D.Wu).
文摘Two rare lyconadin-type Lycopodium alkaloids,lyconadins G(1)and H(2),together with four known ones(3–6),were isolated from Lycopodium complanatum.The structures were determined on the basis of their spectroscopic analyses,and the absolute configuration of 1 was established by an X-ray crystallographic analysis.It is the first time to establish the absolute configuration of lyconadin-type Lycopodium alkaloid by an X-ray diffraction experiment.In addition,these findings may provide more information for the biosynthesis of lyconadins.
基金supported by the National Natural Science Foundation of China(No.21837003)Open fund from the State Key Laboratory of Phytochemistry and Plant Resources in West China(No.P2017-KF13)
文摘Lycophytes and ferns are unique and charismatic members of many terrestrial ecosystems and occupy the pivotal position in land plant origin and evolution.The Chinese lycophytes and ferns flora,with approximately 2000 species,contributes a substantial component to the global lycophytes and ferns diversity,with estimates of 12000 species.Among them,about 433 species are medicinally recorded and researches based on their phytochemical properties are important topics in natural medicines.This paper reviewed the research history and current status of chemical constituents and biological activities of lycophytes and ferns,which had highlighted the research progress of our group.
基金supported by the NSFC-Joint Foundation of Yunnan Province(No.U1502223)the National Natural Science Foundation of China(Nos.81773611 and 21602227)the Science and Technology Program of Yunnan province(Nos.2016FB140 and 2015FB173).
文摘A novel Ci7N Lycopodium alkaloid(LA),lycoplanine B(1),containing an unusual formyl group,along with two new LAs,lycoplanines C(2)and D(3),were isolated from the whole plant of Lycopodium complanatum.Their structures were elucidated by extensive NMR techniques,including 1D-and 2D-NMR experiments,as well as comparing their spectral data with those of the known analogues.A possible biogenetic pathway for 1 was also proposed.
基金Supported by Dongguk University Research Fund of 2015
文摘Objectives： To elucidate how ethanol extract of L. serratum（ELS） could exert anti-migratory effects on glioma with the suppression of nuclear factor kappa B（NF-κB） downstream pathway. Methods： Cell viability of ELS on C6 glioma was detected by 3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay. Nitric oxide（NO） assay and 2＇,7＇-dichlorofluorescin diacetate（DCFH-DA） assay were applied to measure NO production and reactive oxygen species（ROS） generation on lipopolysaccharide（LPS）-induced C6 glioma cells. NF-κB, mitogen-activated protein kinase（MAPK）, inducible nictric oxide synthase（i NOS） and cyclooxygenase-2（COX-2） protein were determined by Western blot. Wound healing assay was used to investigate the inhibitory effect of ELS on fetal bovine serum（FBS）-induced migration and matrix metalloproteinase（MMP）-9 and-2 activity was examined by zymography. Results： ELS suppressed LPS-induced phosphorylation of extracellular signal-regulated kinase（ERK）, c-Jun N-terminal kinase（JNK）, and p38 through inhibiting the expression of chemokine CCL2（or monocyte chemoattractant protein-1, MCP-1）. In addition, ELS inhibited the expression of i NOS, COX-2, and the production of NO by LPS in C6 glioma cells. ELS also significantly decreased serum-induced migration of C6 glioma cells in scratch wound healing in a dose-dependent manner（P〈0.01）. The activity of MMP-9 and-2 were also significantly attenuated by ELS with LPS treatment（P〈0.01）. Conclusion： Our results suggest that downregulation of MMP-9 gene expression might be involved in the anti-migration effect of ELS against LPS-induced C6 glioma cells.
基金the National Natural Science Foundation of China(Nos.90813004 and U0932602)the National Basic Research Program of China(973 Program No.2011CB915503).
文摘Three new lycopodine-type alkaloids,4a-hydroxyanhydrolycodoline(1),4a,6a-dihydroxyanhydrolycodoline(2),and 6-epi-8b-acetoxylycoclavine(3),and an artifact,lycoposerramine G nitrate(4),along with seventeen related known compounds,were isolated from the club moss Lycopodium japonicum Thunb.ex Murray(Lycopodiaceae).Their structures were elucidated by extensive spectroscopic methods as well as X-ray analysis.Compounds 1–4 were evaluated for their acetylcholine esterase inhibitory activity.
文摘Two novel hydroperoxylated Lycopodium alkaloids, 11alpha-hydroperoxyphlegmariurine B (1) and 7-hydroperoxyphlegmariurine B (2), along with a known compound, phlegmanurine B (3), were isolated from the total alkaloid fraction of the Chinese medicinal herb Huperzia serrata (Thunb.) Trev. Their structures and relative configurations were elucidated on the basis of spectroscopic analyses.
基金the NSFC-Joint Foundation of Yunnan Province(No.U1502223)the National Natural Science Foundation of China(No.21402212)+1 种基金the Science and Technology Program of Yunnan province(No 2015FB173)the CAS"Light of West China"Program and Youth Innovation Promotion Association CAS(X.D.Wu).
文摘t Three new lycodine-type Lycopodium alkaloids,namely 1-methyllycodine(1),8a-hydroxy-15,16-dehydro-desN-methyl-a-obscurine(2),N-methyl-16-hydroxyhuperzine B(3),and one new natural lycodine-type Lycopodium alkaloid,N-methylhuperzine A(4),along with 11 known analogues(5–15),were isolated from the whole plants of club moss Huperzia serrata.The structures of 1–4 were elucidated on the basis of NMR spectroscopic and mass spectrometry data.Among them,compound 1 was the first lycodine-type alkaloid possessing a methyl group at C-1.In addition,the structure of 5 was confirmed by the single-crystal X-ray crystallography data and its^(13)C NMR was reported for the first time in current study.Compounds 1–5 were tested their BACE1 inhibitory activity.
