Two lindenane-type sesquiterpene(LDS)trimers with unprecedented carbon skeletons,holotrichones A(1)and B(2),were obtained from the whole plant of Chloranthus holostegius var.trichoneurus by a ultra performance liquid ...Two lindenane-type sesquiterpene(LDS)trimers with unprecedented carbon skeletons,holotrichones A(1)and B(2),were obtained from the whole plant of Chloranthus holostegius var.trichoneurus by a ultra performance liquid chromatography-photodiode array detector-mass spectrometry(UPLC-PDA-MS)-guided isolation strategy.Compound 1 represents the first LDS trimer incorporating a unique 3/5/6/6-fused framework,in which a lindenane-type monomer and the 2-methylbutyryl substituent of an LDS dimer is bridged by a six-membered ring system.Compound 2 is the first hetero-trimer fused by an LDS dimer with a p-benzoquinone-meroterpenoid,featuring an unusual 3/5/6/6/3/5/6/6/6 nonacyclic system fused by the sesquiterpenoid unit and a 2-geranyl-6-methyl-2,5-cyclohexadien-1,4-dione moiety.In compound 2,the dimeric LDS moiety is equipped with a rare oxaspiro[4.5]decane system.Their structures,including absolute configurations,were established by spectroscopic methods,GIAO NMR calculations and DP4+probability analyses,electronic circular dichroism(ECD)calculations,and single-crystal X-ray diffraction analysis.The plausible biogenetic pathway speculation indicated that hetero-and homo-DielsAlder additions may dominate the formation of these highly fused polycyclic frameworks.Both compounds 1 and 2 induced the human acute myeloid leukemia MV-4–11 cell death via apoptosis induction,which deserves further investigation on this new chemical class of LDS oligomers for their anti-leukemic potential.展开更多
An investigation toward the synthesis of the lindenane-type sesquiterpenoid monomer of Chlorahololide A using a Yamamoto rearrangement, intramolecular cyclopropanation reaction, 1,3-dipolar cyclization, and an intra- ...An investigation toward the synthesis of the lindenane-type sesquiterpenoid monomer of Chlorahololide A using a Yamamoto rearrangement, intramolecular cyclopropanation reaction, 1,3-dipolar cyclization, and an intra- molecular Heck reaction gave the pivotal intermediate 20. This gives a practical synthetic route that could generate further natural products of the Chloranthaceae family.展开更多
Sarcandra glabra(Thunb.)Nakai is a perennial evergreen herb categorised within the Sarcandra Gardner genus under the Chloranthaceae family.Indigenous to tropical and subtropical regions of East Asia and India,this spe...Sarcandra glabra(Thunb.)Nakai is a perennial evergreen herb categorised within the Sarcandra Gardner genus under the Chloranthaceae family.Indigenous to tropical and subtropical regions of East Asia and India,this species is extensively distributed across China,particularly in the southern regions(Sichuan,Yunnan,and Jiangxi).In addition to its high ornamental value,S.glabra has a rich history of use in traditional Chinese medicine,evident through its empirical prescriptions for various ailments like pneumonia,dysentery,fractures,bruises,numbness,amenorrhea,rheumatism,and other diseases.Besides,modern pharmacological studies have revealed various biological activities,such as antitumour,anti-bacterial,anti-viral anti-inflammatory and immunomodulatory effects.The diverse chemical constituents of S.glabra have fascinated natural product researchers since the 1900s.To date,over 400 compounds including terpenoids,coumarins,lignans,flavonoids,sterols,anthraquinones,organic acids,and organic esters have been isolated and characterised,some featuring unprecedented structures.This review comprehensively examines the current understanding of S.glabra’s phytochemistry and pharmacology,with emphasis on the chemistry and biosynthesis of its unique chemotaxonomic marker,the lindenane-type sesquiterpenoids.展开更多
Seventeen undescribed lindenane-related sesquiterpenoid dimers,chlorajaponins A—Q(1—17),and 13 reported analogs(18—30)were isolated from Chloranthus japonicus Sieb.Compound 1 possesses an unprecedented 3/5/7/5/5/6/...Seventeen undescribed lindenane-related sesquiterpenoid dimers,chlorajaponins A—Q(1—17),and 13 reported analogs(18—30)were isolated from Chloranthus japonicus Sieb.Compound 1 possesses an unprecedented 3/5/7/5/5/6/5/3 fused octacyclic scaffold,featuring a 6(5→4)-abeo-lindenane monomer,while 2 exhibits a 3/5/6/6/5/6/5/3 fused octacyclic scaffold.Their structures were determined through a combination of spectroscopic analyses and X-ray crystallography.Compounds 1,2,and 18 demonstrated significant inhibitory effects on lipid accumulation and effectively reduced the levels of triglycerides and total cholesterol,as well as the levels of aspartate aminotransferase and alanine aminotransferase in a HepG2 cell model.In addition,compounds 1,2,and 18 significantly suppressed the protein expression of the fatty acid synthase(FASN)and the sterol regulatory element-binding protein 1(SREBP1).Moreover,the anti-inflammatory assay showed that compounds 19—22 and 25 inhibited the NO production induced by lipopolysaccharide in RAW 264.7 macrophages with IC50 values of 7.89±0.44,6.25±0.46,2.98±0.29,10.77±0.60,and 3.60±0.28μmol/L.展开更多
基金supported by grants from the National Natural Science Foundation of China(Nos.21772025,21937002)。
文摘Two lindenane-type sesquiterpene(LDS)trimers with unprecedented carbon skeletons,holotrichones A(1)and B(2),were obtained from the whole plant of Chloranthus holostegius var.trichoneurus by a ultra performance liquid chromatography-photodiode array detector-mass spectrometry(UPLC-PDA-MS)-guided isolation strategy.Compound 1 represents the first LDS trimer incorporating a unique 3/5/6/6-fused framework,in which a lindenane-type monomer and the 2-methylbutyryl substituent of an LDS dimer is bridged by a six-membered ring system.Compound 2 is the first hetero-trimer fused by an LDS dimer with a p-benzoquinone-meroterpenoid,featuring an unusual 3/5/6/6/3/5/6/6/6 nonacyclic system fused by the sesquiterpenoid unit and a 2-geranyl-6-methyl-2,5-cyclohexadien-1,4-dione moiety.In compound 2,the dimeric LDS moiety is equipped with a rare oxaspiro[4.5]decane system.Their structures,including absolute configurations,were established by spectroscopic methods,GIAO NMR calculations and DP4+probability analyses,electronic circular dichroism(ECD)calculations,and single-crystal X-ray diffraction analysis.The plausible biogenetic pathway speculation indicated that hetero-and homo-DielsAlder additions may dominate the formation of these highly fused polycyclic frameworks.Both compounds 1 and 2 induced the human acute myeloid leukemia MV-4–11 cell death via apoptosis induction,which deserves further investigation on this new chemical class of LDS oligomers for their anti-leukemic potential.
基金Acknowledgement This work was supported by The National Natural Science Foundation of China （Nos. 30725049, 81021062, 81072652）.
文摘An investigation toward the synthesis of the lindenane-type sesquiterpenoid monomer of Chlorahololide A using a Yamamoto rearrangement, intramolecular cyclopropanation reaction, 1,3-dipolar cyclization, and an intra- molecular Heck reaction gave the pivotal intermediate 20. This gives a practical synthetic route that could generate further natural products of the Chloranthaceae family.
文摘Sarcandra glabra(Thunb.)Nakai is a perennial evergreen herb categorised within the Sarcandra Gardner genus under the Chloranthaceae family.Indigenous to tropical and subtropical regions of East Asia and India,this species is extensively distributed across China,particularly in the southern regions(Sichuan,Yunnan,and Jiangxi).In addition to its high ornamental value,S.glabra has a rich history of use in traditional Chinese medicine,evident through its empirical prescriptions for various ailments like pneumonia,dysentery,fractures,bruises,numbness,amenorrhea,rheumatism,and other diseases.Besides,modern pharmacological studies have revealed various biological activities,such as antitumour,anti-bacterial,anti-viral anti-inflammatory and immunomodulatory effects.The diverse chemical constituents of S.glabra have fascinated natural product researchers since the 1900s.To date,over 400 compounds including terpenoids,coumarins,lignans,flavonoids,sterols,anthraquinones,organic acids,and organic esters have been isolated and characterised,some featuring unprecedented structures.This review comprehensively examines the current understanding of S.glabra’s phytochemistry and pharmacology,with emphasis on the chemistry and biosynthesis of its unique chemotaxonomic marker,the lindenane-type sesquiterpenoids.
基金supported by the National Natural Science Foundation of China(Nos.22177044 and 22077058)The computational resources of this work were supported by the Supercomputing Center of Lanzhou University(China).
文摘Seventeen undescribed lindenane-related sesquiterpenoid dimers,chlorajaponins A—Q(1—17),and 13 reported analogs(18—30)were isolated from Chloranthus japonicus Sieb.Compound 1 possesses an unprecedented 3/5/7/5/5/6/5/3 fused octacyclic scaffold,featuring a 6(5→4)-abeo-lindenane monomer,while 2 exhibits a 3/5/6/6/5/6/5/3 fused octacyclic scaffold.Their structures were determined through a combination of spectroscopic analyses and X-ray crystallography.Compounds 1,2,and 18 demonstrated significant inhibitory effects on lipid accumulation and effectively reduced the levels of triglycerides and total cholesterol,as well as the levels of aspartate aminotransferase and alanine aminotransferase in a HepG2 cell model.In addition,compounds 1,2,and 18 significantly suppressed the protein expression of the fatty acid synthase(FASN)and the sterol regulatory element-binding protein 1(SREBP1).Moreover,the anti-inflammatory assay showed that compounds 19—22 and 25 inhibited the NO production induced by lipopolysaccharide in RAW 264.7 macrophages with IC50 values of 7.89±0.44,6.25±0.46,2.98±0.29,10.77±0.60,and 3.60±0.28μmol/L.
