RESUMO
Two novel prenylated acetophenones with new carbon skeletons, acronyrones A and B (1 and 2), and a new analogue, acronyrone C (3), together with two known compounds (4 and 5) were isolated from the leaves of Acronychia pedunculata. Their structures with absolute configurations were identified by interpretation of spectroscopic data, single crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 1 and 2 represent the first example of prenylated acetophenones possessed a C7 (1) and a C6 (2) side chain, forming a 4-isobutylchroman-2-one unit and a 3-(2-methylpropylidene)benzofuran-2(3H)-one moiety with the acetophenone core, respectively. In addition, compound 4 exhibited significant dose-dependent transcriptional activation effect against retinoid X receptor-α (RXRα), and could be regarded as a new type of non-classical RXR ligand.
Assuntos
Rutaceae , Thoracica , Animais , Estrutura Molecular , Rutaceae/química , Acetofenonas/química , Folhas de Planta/químicaRESUMO
Four pairs of cinnamoyl-ß-triketone derivative enantiomers, (+)- and (-)-xanthostones A-D ((+)- and (-)-1-4), were isolated from Xanthostemon chrysanthus. Compounds 1 and 2 feature a new rearranged cinnamoyl-phloroglucinol scaffold fused with a cinnamyl-ß-triketone framework. Compounds 1, 3, and 4 are the first examples of natural products with a peculiar phenethyl-pyranone acid unit. Their structures with absolute configurations were determined by spectroscopic data, X-ray diffraction analysis and electronic circular dichroism (ECD) calculation. Interestingly, these novel compounds showed a tautomeric behavior in solution, which was revealed by NMR spectroscopy and density functional theory calculation. A plausible biosynthetic pathway toward xanthostones A-D was proposed. Additionally, the anti-inflammatory and antibacterial activities of xanthostones A-D were evaluated.
Assuntos
Myrtaceae , Anti-Inflamatórios , Dicroísmo Circular , Estrutura Molecular , Myrtaceae/química , Floroglucinol/química , EstereoisomerismoRESUMO
Leptosparones A-F (1-6), six new dimeric acylphloroglucinol derivatives with unprecedented skeletons, were isolated from Leptospermum scoparium. Compounds 1-3 and 5-6 are phenylpropanoyl-phloroglucinol dimers, while 4 is a phenylpropanoylphloroglucinol-isovalerylphloroglucinol hybrid. Structurally, these compounds represent the first examples of dimeric phloroglucinols with unprecedented C(7')-C(8) linkage between the phloroglucinol core and the acyl side chain. Their structures were elucidated by comprehensive analyses of spectroscopic data, single crystal X-ray diffraction and chemical calculations. In addition, all compounds showed inhibitory effects against α-glucosidase with IC50 values ranging from 39.5 to 186.8â µM.
Assuntos
Inibidores de Glicosídeo Hidrolases/farmacologia , Leptospermum/química , Floroglucinol/farmacologia , alfa-Glucosidases/metabolismo , Cristalografia por Raios X , Relação Dose-Resposta a Droga , Inibidores de Glicosídeo Hidrolases/síntese química , Inibidores de Glicosídeo Hidrolases/química , Humanos , Modelos Moleculares , Estrutura Molecular , Floroglucinol/síntese química , Floroglucinol/químicaRESUMO
Two novel monoterpenoid indole alkaloids (MIAs), gelsechizines A-B (1-2), along with four known ones (3-6) were isolated from the fruits of Gelsemium elegans. Compound 1 features a new carbon skeleton with two additional carbon atoms forming a 4-methylpyridine unit. Their structures with absolute configurations were elucidated by NMR, MS, X-ray diffraction and electronic circular dichroism (ECD) calculations. Compounds 1-3 showed significant anti-inflammatory effects in vivo and in vitro, which may be related to the inhibition of the trecruitment of neutrophils and macrophages as well as the secretion of TNF-α and IL-6. Preliminary structure-activity relationship analysis revealed that the ß-N-acrylate moiety plays an important role in the anti-inflammatory effect.
Assuntos
Anti-Inflamatórios/farmacologia , Gelsemium/química , Macrófagos/efeitos dos fármacos , Alcaloides de Triptamina e Secologanina/química , Animais , Animais Geneticamente Modificados/crescimento & desenvolvimento , Animais Geneticamente Modificados/metabolismo , Anti-Inflamatórios/química , Anti-Inflamatórios/isolamento & purificação , Frutas/química , Frutas/metabolismo , Gelsemium/metabolismo , Interleucina-6/metabolismo , Larva/efeitos dos fármacos , Larva/crescimento & desenvolvimento , Larva/metabolismo , Lipopolissacarídeos/farmacologia , Macrófagos/citologia , Macrófagos/metabolismo , Espectroscopia de Ressonância Magnética , Camundongos , Conformação Molecular , Neutrófilos/citologia , Neutrófilos/patologia , Células RAW 264.7 , Alcaloides de Triptamina e Secologanina/isolamento & purificação , Alcaloides de Triptamina e Secologanina/farmacologia , Relação Estrutura-Atividade , Fator de Necrose Tumoral alfa/metabolismo , Peixe-Zebra/crescimento & desenvolvimento , Peixe-Zebra/metabolismoRESUMO
Myrcauones A-D (1-4), four new phloroglucinol-terpene adducts were isolated from the leaves of Myrciaria cauliflora. Their structures with absolute configurations were elucidated by combination of spectroscopic analysis, single crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compound 1 was a rearranged isobutylphloroglucinol-pinene adduct featuring an unusual 2,3,4,4a,10,11-hexahydro-1H-3,11a-methanodibenzo[b,f]oxepin backbone. Compound 4 showed moderate antibacterial activity against Gram-positive bacteria including multiresistant strains.
RESUMO
Myrtucyclitones A-C ((+)- and (-)-1-3), three pairs of new triketone-phloroglucinol-triketone hybrids were isolated from the plant Myrtus communis. Their structures with absolute configurations were established by NMR analysis and chemical calculations. Myrtucyclitones B and C exhibited remarkable antibacterial effect.
Assuntos
Antibacterianos/química , Cetonas/química , Myrtus/química , Floroglucinol/química , Antibacterianos/isolamento & purificação , Antibacterianos/farmacologia , Dicroísmo Circular , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Espectroscopia de Ressonância Magnética , Testes de Sensibilidade Microbiana , Conformação Molecular , Myrtus/metabolismo , Folhas de Planta/química , Folhas de Planta/metabolismo , Caules de Planta/química , Caules de Planta/metabolismoRESUMO
Three rearranged triketone-terpene adducts, myrcaulones A-C (1-3), were isolated from the leaves of Myrciaria cauliflora. Myrcaulones A (1) and B (2) feature a new carbon skeleton with an unprecedented spiro[bicyclo[3.1.1]heptane-2,2'-cyclopenta[b]pyran] core. Myrcaulone C (3) possesses an unusual cyclobuta[6,7]cyclonona[1,2-b]cyclopenta[e]pyran backbone. Their structures with absolute configurations were elucidated by NMR spectroscopy, X-ray diffraction, and electronic circular dichroism calculations. A plausible biogenetic pathway for myrcaulones A-C involving the rearrangement of a triketone unit is also proposed. In addition, myrcaulones A (1) and B (2) exhibited inhibitory effects against tumor necrosis factor-α and nitric oxide generation induced by lipopolysaccharide in RAW 264.7 macrophages.
Assuntos
Cetonas/química , Myrtaceae/química , Terpenos/química , Folhas de Planta/química , Análise Espectral/métodosRESUMO
Myrtucomvalones D-F, three new triketone-phloroglucinol-triketone adducts, and three known ones (myrtucommulone E, myrtucommulone D and callistenone D) were obtained from Myrtus communis 'Variegata'. Myrtucomvalone D is a pair of enantiomers which was further resolved into (+)-myrtucomvalone D and (-)-myrtucomvalone D by chiral HPLC. Their structures and complete stereochemistry were established from interpretation of NMR and crystallographic data and chemical calculations. Myrtucomvalone F, myrtucommulone D and callistenone D showed significant antibacterial activities.
Assuntos
Antibacterianos/farmacologia , Myrtus/química , Floroglucinol/farmacologia , Bactérias/efeitos dos fármacos , Cromatografia Líquida de Alta Pressão , Testes de Sensibilidade Microbiana , Floroglucinol/química , Folhas de Planta/química , Análise Espectral/métodosRESUMO
Leptosperols A and B (1 and 2), two cinnamoylphloroglucinol-sesquiterpenoid hybrids featuring unprecedented 1-benzyl-2-(2-phenylethyl) cyclodecane and 2-benzyl-3-phenylethyl decahydronaphthalene backbones, along with their biosynthetic precursor (3), were isolated from Leptospermum scoparium. Compounds 1 and 2 represent the first example of phloroglucinol derivatives biogenetically constructed by a De Mayo reaction. The biomimetic synthesis of leptosperol B (2) was achieved using the proposed biosynthetic pathway. In addition, compounds 1 and 2 showed significant anti-inflammatory effects in zebrafish acute inflammatory models.
Assuntos
Leptospermum/química , Floroglucinol/química , Sesquiterpenos/química , Biomimética , Estrutura Molecular , Floroglucinol/análogos & derivados , Sesquiterpenos/síntese químicaRESUMO
(+)- and (-)-Xanchryones F and G ((+)- and (-)-1 and 2) were isolated from the plant Xanthostemon chrysanthus by chiral separation. Compounds 1 and 2 featured a new carbon skeleton with cinnamoyltriketone-flavone adducts. Their structures with absolute configurations were elucidated by detailed spectroscopic analyses and chemical calculations. The antibacterial and anti-inflammatory activities of (+)- and (-)-1 and 2 were evaluated.
Assuntos
Antibacterianos/farmacologia , Anti-Inflamatórios/farmacologia , Cinamatos/farmacologia , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Compostos Heterocíclicos com 2 Anéis/farmacologia , Inflamação/tratamento farmacológico , Myrtaceae/química , Animais , Antibacterianos/química , Antibacterianos/isolamento & purificação , Anti-Inflamatórios/química , Anti-Inflamatórios/isolamento & purificação , Cinamatos/química , Cinamatos/isolamento & purificação , Compostos Heterocíclicos com 2 Anéis/química , Compostos Heterocíclicos com 2 Anéis/isolamento & purificação , Lipopolissacarídeos/antagonistas & inibidores , Lipopolissacarídeos/farmacologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Testes de Sensibilidade Microbiana , Conformação Molecular , Óxido Nítrico/antagonistas & inibidores , Óxido Nítrico/biossíntese , Células RAW 264.7 , EstereoisomerismoRESUMO
Three pairs of dimeric phenylpropanoyl-phloroglucinol enantiomers, (+)- and (-)-xanthchrysones A-C [(+)- and (-)-1-3], as well as their postulated biosynthetic precursors, were isolated and identified from the leaves of Xanthostemon chrysanthus. Compound 1 featured an unprecedented bis-phenylpropanoyl-benzo[b]cyclopent[e] oxepine tricyclic backbone. Compounds 2 and 3 represent the first examples of 1-(cyclopentylmethyl)-3-(3-phenylpropanoyl)benzene scaffold. The structures and absolute configurations of 1-3 were determined by spectroscopic and X-ray diffraction analysis as well as electronic circular dichroism (ECD) calculation. Both (+)-2 and (-)-2 showed moderate antibacterial activities including several multidrug-resistant strains.
Assuntos
Myrtaceae/química , Fenilpropionatos/química , Floroglucinol/química , Dimerização , Modelos Moleculares , Estrutura Molecular , EstereoisomerismoRESUMO
Callistrilones F - K (1 - 6), six new triketone-phloroglucinol-monoterpene hybrids were isolated from the twigs and leaves of Callistemon rigidus. Their structures with absolute configurations were established by a combination analysis of NMR spectra, X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 3 and 4 exhibited moderate inhibitory activities against herpes simplex virus (HSV-1) with IC50 values of 10.00 ± 2.50 and 12.50 ± 1.30 µm, respectively.
Assuntos
Antivirais/farmacologia , Cetonas/farmacologia , Monoterpenos/farmacologia , Myrtaceae/química , Floroglucinol/farmacologia , Simplexvirus/efeitos dos fármacos , Antivirais/química , Antivirais/isolamento & purificação , Relação Dose-Resposta a Droga , Cetonas/química , Cetonas/isolamento & purificação , Testes de Sensibilidade Microbiana , Conformação Molecular , Monoterpenos/química , Monoterpenos/isolamento & purificação , Floroglucinol/química , Floroglucinol/isolamento & purificação , Estereoisomerismo , Relação Estrutura-AtividadeRESUMO
Four new cinnamoyl-phloroglucinols (1-4) were isolated from the leaves of Xanthostemon chrysanthus. Compounds 1 and 2 represent the first example of natural phloroglucinols with an oxazole unit. Their structures were elucidated on the basis of NMR spectroscopic data and single crystal X-ray diffraction. Compound 3 showed moderate cytotoxic activity against MDA-MB-231 and SGC-7901 cells with IC50 values of 25.26⯱â¯0.35⯵M and 31.2⯱â¯0.94⯵M, respectively.
Assuntos
Myrtaceae/química , Floroglucinol/isolamento & purificação , Folhas de Planta/química , Antineoplásicos Fitogênicos/isolamento & purificação , Antineoplásicos Fitogênicos/farmacologia , Linhagem Celular Tumoral , Humanos , Estrutura Molecular , Floroglucinol/farmacologiaRESUMO
Five monoterpenoid bisindole alkaloids with new carbon skeletons, gelsecorydines A-E (1-5), together with their biogenetic precursors were isolated from the fruits of Gelsemium elegans. Compounds 1-5 represent the first examples of heterodimeric frameworks composed of a gelsedine-type alkaloid and a modified corynanthe-type one. Notably, compound 2 featured an unprecedented caged skeleton with a 6/5/7/6/5/6 heterohexacyclic ring system, which possessed a pyridine ring that linked the two monomers. Their structures and absolute configurations were elucidated by spectroscopic analysis, X-ray diffraction, and electronic circular dichroism (ECD) calculation. A plausible biosynthetic pathway for compounds 1-5 is proposed. Compounds 1, 3, 4, and 5 exhibited a significant inhibitory effect against nitric oxide (NO) production in macrophages.
Assuntos
Alcaloides/química , Frutas/química , Gelsemium/química , Indóis/química , Alcaloides/isolamento & purificação , Alcaloides/farmacologia , Animais , Dicroísmo Circular , Cristalografia por Raios X , Relação Dose-Resposta a Droga , Indóis/isolamento & purificação , Indóis/farmacologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Modelos Moleculares , Conformação Molecular , Óxido Nítrico/antagonistas & inibidores , Óxido Nítrico/biossíntese , Teoria Quântica , Células RAW 264.7 , Relação Estrutura-AtividadeRESUMO
Two pairs of atropisomeric bisindole alkaloids, gelsekoumidines A (1) and B (2), with a new carbon skeleton, were isolated from the roots of Gelsemium elegans. Compounds 1 and 2 represent the first examples of seco-koumine-gelsedine type alkaloids, which feature an unprecedented 20,21-seco-koumine scaffold fused with a gelsedine framework via a double bond. Their structures including absolute stereochemistry were elucidated by spectroscopic data, single-crystal X-ray diffraction, and electronic circular dichroism (ECD) calculation. A plausible biogenetic pathway for the new compounds is also proposed. Compound 2 exhibited a moderate inhibitory effect against nitric oxide (NO) production.
Assuntos
Gelsemium , Alcaloides , Dicroísmo Circular , Estrutura Molecular , Raízes de PlantasRESUMO
Five new koumine-type alkaloids (1-5) along with six known ones were isolated from the roots of Gelsemium elegans. Their structures with absolute configurations were elucidated on the basis of NMR spectroscopy and electronic circular dichroism spectral analyses. The inhibitory effects of compounds 1-11 on the viability of three tumor cell lines (A-649, HepG2, and HuH7) were evaluated by the MTT assay.