AIM: To study the 9, 19-cycloartane triterpenes from the roots of Cimicifuga foetida. METHOD: Chromatographic separations by silica gel, C18 reversed phase silica gel, and high-performance liquid chromatography(HPLC) ...AIM: To study the 9, 19-cycloartane triterpenes from the roots of Cimicifuga foetida. METHOD: Chromatographic separations by silica gel, C18 reversed phase silica gel, and high-performance liquid chromatography(HPLC) were used. All of the structures were elucidated on the basis of spectroscopic analysis and chemical methods. RESULTS: Five 9, 19-cycloartane triterpenes,(3β, 12β, 15α, 24R)-12, 2'-diacetoxy-24, 25-epoxy-15-hydroxy-16, 23-dione-3-O-α-L-arabinopyranoside(1), actein(2), 23-epi-26-deoxyactein(3), asiaticoside B(4), and 12β-hydroxycimigenol(5) were isolated from the roots of Cimicifuga foetida. CONCLUSION: Compound 1 is a new triterpene with two acetoxy groups at C-2' and C-12.展开更多
Hammett constants,a popular tool for predicting substitution effects on chemical reactivity and catalytic activity,the binding affinity of drugs and the spin-crossover(SCO)behavior of metal complexes,are frequently cr...Hammett constants,a popular tool for predicting substitution effects on chemical reactivity and catalytic activity,the binding affinity of drugs and the spin-crossover(SCO)behavior of metal complexes,are frequently criticized.Among others,they define the acetoxy group as electron-withdrawing(EWG),although it activates electrophilic substitution in the benzene ring as an electron donor(EDG).We argue that SCO compounds provide an excellent platform for reevaluating Hammett constants,with the SCO midpoint temperature as a quantitative measure of even subtle changes in organic ligands.For a new series of iron(Ⅱ)complexes of bis(pyrazol-3-yl)pyridines(3-bpp),this measure showed a contradictory increase induced by both EWGs and EDGs.Yet,it correlated linearly with NMR chemical shifts,metal-ligand bond lengths and energies.Together,these correlations yielded Hammett constants that correctly identified the acetoxy group as an EDG,among others.The new constants allowed us not only to explain the SCO behaviour of metal complexes with 3-bpp and other popular families of N-donor ligands but also to predict the SCO midpoint temperature with high accuracy.Beyond the SCO realm,they were extended to rationalize the outcomes of Diels-Alder and polymerization reactions.By using metal-ligand bond lengths routinely measured for coordination compounds,Hammett constants can be further‘refined’to help design new,more efficient catalysts,drugs and materials for advanced applications in quantum technologies and(bio)sensing,energy conversion and smart/self-healing coatings.展开更多
基金supported by the National Natural Science Foundation of China(No.U1132604)Knowledge Innovation Program of the CAS(No.KZCX2-XB2-15-03)Foundation of State Key Laboratory of Phytochemistry and Plant Resources in West China(P2008-ZZ05)
文摘AIM: To study the 9, 19-cycloartane triterpenes from the roots of Cimicifuga foetida. METHOD: Chromatographic separations by silica gel, C18 reversed phase silica gel, and high-performance liquid chromatography(HPLC) were used. All of the structures were elucidated on the basis of spectroscopic analysis and chemical methods. RESULTS: Five 9, 19-cycloartane triterpenes,(3β, 12β, 15α, 24R)-12, 2'-diacetoxy-24, 25-epoxy-15-hydroxy-16, 23-dione-3-O-α-L-arabinopyranoside(1), actein(2), 23-epi-26-deoxyactein(3), asiaticoside B(4), and 12β-hydroxycimigenol(5) were isolated from the roots of Cimicifuga foetida. CONCLUSION: Compound 1 is a new triterpene with two acetoxy groups at C-2' and C-12.
基金supported by the Russian Science Foundation(project 24-73-00165)the equipment of the Center for Collective Use of INEOS RAS with support from the Ministry of Science and Higher Education of the Russian Federation(contract/agreement supported by the Russian Science Foundation(project 24-73-00165)+1 种基金performed using the equipment of the Center for Collective Use of INEOS RAS with support from the Ministry of Science and Higher Education of the Russian Federation(contract/agreement no.075-00276-25-00)the support of the Spanish Ministry of Science(grant BG22/00039).
文摘Hammett constants,a popular tool for predicting substitution effects on chemical reactivity and catalytic activity,the binding affinity of drugs and the spin-crossover(SCO)behavior of metal complexes,are frequently criticized.Among others,they define the acetoxy group as electron-withdrawing(EWG),although it activates electrophilic substitution in the benzene ring as an electron donor(EDG).We argue that SCO compounds provide an excellent platform for reevaluating Hammett constants,with the SCO midpoint temperature as a quantitative measure of even subtle changes in organic ligands.For a new series of iron(Ⅱ)complexes of bis(pyrazol-3-yl)pyridines(3-bpp),this measure showed a contradictory increase induced by both EWGs and EDGs.Yet,it correlated linearly with NMR chemical shifts,metal-ligand bond lengths and energies.Together,these correlations yielded Hammett constants that correctly identified the acetoxy group as an EDG,among others.The new constants allowed us not only to explain the SCO behaviour of metal complexes with 3-bpp and other popular families of N-donor ligands but also to predict the SCO midpoint temperature with high accuracy.Beyond the SCO realm,they were extended to rationalize the outcomes of Diels-Alder and polymerization reactions.By using metal-ligand bond lengths routinely measured for coordination compounds,Hammett constants can be further‘refined’to help design new,more efficient catalysts,drugs and materials for advanced applications in quantum technologies and(bio)sensing,energy conversion and smart/self-healing coatings.
