Three new C20-diterpenoid alkaloids, designated as anthriscifolmines A-C (1-3), together with two known alkaloids denudatine and delgramine, were isolated from the whole herb of Delphinium anthriscifolium var. savat...Three new C20-diterpenoid alkaloids, designated as anthriscifolmines A-C (1-3), together with two known alkaloids denudatine and delgramine, were isolated from the whole herb of Delphinium anthriscifolium var. savatieri. The structures of these new alkaloids were elucidated on the basis of spectral data.展开更多
Two sulfo nated seco C_(20)-diterpenoid alkaloids,aconapelsulfonines A(1) and B(2),were isolated from an aqueous extract of the raw material of "Fu Zi"(the Aconitum carmichaelii lateral roots),of which the s...Two sulfo nated seco C_(20)-diterpenoid alkaloids,aconapelsulfonines A(1) and B(2),were isolated from an aqueous extract of the raw material of "Fu Zi"(the Aconitum carmichaelii lateral roots),of which the structures were elucidated by various spectroscopic data,combined with X-ray crystallogra phic analysis.The unprecedented skeletons are biogenetically proposed to be derived via Criegee rearrangements of the napelline-type architecture.The two compounds exhibited dose-depended analgesic activities on an acetic acid-induced mice writhing test.展开更多
Three new napelline-type C20-diterpenoid alkaloids,named aconicarmichinium A and B trifluoroacetates(1 and 2) and aconicarmichinium C chloride(3),were isolated from an aqueous extract of "fu zi",the lateral root...Three new napelline-type C20-diterpenoid alkaloids,named aconicarmichinium A and B trifluoroacetates(1 and 2) and aconicarmichinium C chloride(3),were isolated from an aqueous extract of "fu zi",the lateral roots of Aconitum carmichaelii.Their structures were elucidated by extensive spectroscopic data analysis.Compounds 1-3 represent the first examples of napelline-type C20 diterpenoid alkaloid alcohol iminiums,of which the structures were fully characterized.In addition,transformation and equilibration between the alcohol iminiums(1-3) and the aza acetals la-3a were investigated by measurements of the NMR spectra in protic and aprotic deuterium solvents including alkali pyridine-d5,along with evaporation under reduced pressure and gradual additions of TFA,AcOH,and HC1.The results demonstrated that the transformation and equilibration were solvent-,base-,and acid-dependent.Especially,in aqueous biological fluid,these C20-diterpenoid alkaloids would more likely exist as the alcohol iminiums accompanied by anion counterparts in biosystems to increase their solubility, bioavailability, transportations, and functions.The absolute configurations of 1-3 were confirmed by X-ray crystallographic analysis of 2a.展开更多
A bicyclo[2.2.2]octane C/D ring system, with a lactonic ring at C-8 and C-9, of the atisine-type C20-diterpenoid alkaloids, was successfully synthesized, using an oxidative dearomatization/intramolecular Diels-Alder r...A bicyclo[2.2.2]octane C/D ring system, with a lactonic ring at C-8 and C-9, of the atisine-type C20-diterpenoid alkaloids, was successfully synthesized, using an oxidative dearomatization/intramolecular Diels-Alder reaction.展开更多
A rare arcutine-type C_(20)-diterpenoid alkaloid, named aconicarmicharcutinium A and obtained as hydroxide(1) and trifluoroacetate(1a), was characterized as a minor constituent of "fu zi"(the lateral roots of...A rare arcutine-type C_(20)-diterpenoid alkaloid, named aconicarmicharcutinium A and obtained as hydroxide(1) and trifluoroacetate(1a), was characterized as a minor constituent of "fu zi"(the lateral roots of Aconitum carmichaelii). The structures of 1 and 1a were elucidated by comprehensive analysis of spectroscopic data including^(19)F and 2D NMR experiments. Compounds 1 and 1a represent the first examples of the arcutine-type C_(20)-diterpenoid alkaloid iminium.展开更多
Three new C20-diterpenoid alkaloids with a sulfonic acid unit,named aconicarmisulfonines B and C(1 and 2)and chuanfusulfonine A(3),respectively,were isolated from the Aconitum carmichaelii lateral roots("fu zi&qu...Three new C20-diterpenoid alkaloids with a sulfonic acid unit,named aconicarmisulfonines B and C(1 and 2)and chuanfusulfonine A(3),respectively,were isolated from the Aconitum carmichaelii lateral roots("fu zi"in Chinese).Structures of 1-3 were determined by spectroscopic data analysis.Intriguing chemical properties and reactions were observed for the C20-diterpenoid alkaloids:(a)specific selective nucleophilic addition of the carbonyl(C-12)in 1 with CD3 OD;(b)interconversion between 1 and 2 in D2 O;(c)stereo-and/or regioselective deuterations of H-11αin 1-3 and both H-11αand H-11βin aconicarmisulfonine A(4);(d)TMSP-2,2,3,3-d4 promoted cleavage of the C-12-C-13 bond of 4 in D2 O;(e)dehydrogenation of 4 in pyridine-d5,and(f)Na2 SO3-assisted dehydrogenation and N-deethylation of songorine(5,a putative precursor of 1-4).Biogenetically,1 and 2 are correlated with 4,for which the same novel carbon skeleton is proposed to be derived from semipinacol rearrangements via migrations of C-13-C-16 and C-15-C-16 bonds of the napelline-type skeleton,respectively.Meanwhile,3 is a highly possible precursor or a concurrent product in the biosynthetic pathways of 1,2,and 4.In the acetic acid-induced mice writhing assay,at 1.0 mg/kg(i.p.),compounds 1,2,5,5 a,and 5 b exhibited analgesic effects against mice writhing.展开更多
Abstract: Two new hetisine-type C20-diterpenoid alkaloids named spiraqine (1) and 6-hydroxylspiraqine (2), and four known alkaloids, namely spiredine (3), spiradine A (4), spiradine B (5), and spirasine V/VI (6), were...Abstract: Two new hetisine-type C20-diterpenoid alkaloids named spiraqine (1) and 6-hydroxylspiraqine (2), and four known alkaloids, namely spiredine (3), spiradine A (4), spiradine B (5), and spirasine V/VI (6), were isolated from Spiraea japonica L. f. var. fortunei(Planchon) Rehd. The structures of the alkaloids were elucidated using nuclear magnetic resonance analysis (1H-NMR, 13C-NMR, DEPT, HMQC, and HMBC) and mass spectrometry data.展开更多
基金supported by the National Natural Science Foundation of China(No.30472075)the Excellent Ph.D.Dissertation Foundation of China(No.200367)
文摘Three new C20-diterpenoid alkaloids, designated as anthriscifolmines A-C (1-3), together with two known alkaloids denudatine and delgramine, were isolated from the whole herb of Delphinium anthriscifolium var. savatieri. The structures of these new alkaloids were elucidated on the basis of spectral data.
基金Financial support from the National Natural Sciences Foundation of China(Nos.81630094 and 81573445)CAMS Innovation Fund for Medical Science(Nos.2017-I2M-3-010,2017-I2M-3-011,and 2016-I2M-1-010)The Drug Innovation Major Project(2018ZX09711001-003-001)is acknowledged。
文摘Two sulfo nated seco C_(20)-diterpenoid alkaloids,aconapelsulfonines A(1) and B(2),were isolated from an aqueous extract of the raw material of "Fu Zi"(the Aconitum carmichaelii lateral roots),of which the structures were elucidated by various spectroscopic data,combined with X-ray crystallogra phic analysis.The unprecedented skeletons are biogenetically proposed to be derived via Criegee rearrangements of the napelline-type architecture.The two compounds exhibited dose-depended analgesic activities on an acetic acid-induced mice writhing test.
基金Financial support from the National Natural Science Foundation of China (NNSFC Nos. 21132009, 30825044)the National Science and Technology Project of China (Nos. 2012ZX09301002002, 2011ZX0 9307-002-01)
文摘Three new napelline-type C20-diterpenoid alkaloids,named aconicarmichinium A and B trifluoroacetates(1 and 2) and aconicarmichinium C chloride(3),were isolated from an aqueous extract of "fu zi",the lateral roots of Aconitum carmichaelii.Their structures were elucidated by extensive spectroscopic data analysis.Compounds 1-3 represent the first examples of napelline-type C20 diterpenoid alkaloid alcohol iminiums,of which the structures were fully characterized.In addition,transformation and equilibration between the alcohol iminiums(1-3) and the aza acetals la-3a were investigated by measurements of the NMR spectra in protic and aprotic deuterium solvents including alkali pyridine-d5,along with evaporation under reduced pressure and gradual additions of TFA,AcOH,and HC1.The results demonstrated that the transformation and equilibration were solvent-,base-,and acid-dependent.Especially,in aqueous biological fluid,these C20-diterpenoid alkaloids would more likely exist as the alcohol iminiums accompanied by anion counterparts in biosystems to increase their solubility, bioavailability, transportations, and functions.The absolute configurations of 1-3 were confirmed by X-ray crystallographic analysis of 2a.
基金the financial support provided by the National Science Foundation of China(No.81273387)
文摘A bicyclo[2.2.2]octane C/D ring system, with a lactonic ring at C-8 and C-9, of the atisine-type C20-diterpenoid alkaloids, was successfully synthesized, using an oxidative dearomatization/intramolecular Diels-Alder reaction.
基金Financial support from the National Natural Science Foundation of China(NNSFCNos.81630094 and 30825044)
文摘A rare arcutine-type C_(20)-diterpenoid alkaloid, named aconicarmicharcutinium A and obtained as hydroxide(1) and trifluoroacetate(1a), was characterized as a minor constituent of "fu zi"(the lateral roots of Aconitum carmichaelii). The structures of 1 and 1a were elucidated by comprehensive analysis of spectroscopic data including^(19)F and 2D NMR experiments. Compounds 1 and 1a represent the first examples of the arcutine-type C_(20)-diterpenoid alkaloid iminium.
基金Financial support of the National Natural Sciences Foundation of China(81630094,21732008,and 81730093)CAMS Innovation Fund for Medical Science of China(2017-I2M-3-010 and 2016I2M-1-010)the Drug Innovation Major Project(2018ZX09711001-001-001,2018ZX09711001-001-003,and 2018ZX09711001-003-001,China)
文摘Three new C20-diterpenoid alkaloids with a sulfonic acid unit,named aconicarmisulfonines B and C(1 and 2)and chuanfusulfonine A(3),respectively,were isolated from the Aconitum carmichaelii lateral roots("fu zi"in Chinese).Structures of 1-3 were determined by spectroscopic data analysis.Intriguing chemical properties and reactions were observed for the C20-diterpenoid alkaloids:(a)specific selective nucleophilic addition of the carbonyl(C-12)in 1 with CD3 OD;(b)interconversion between 1 and 2 in D2 O;(c)stereo-and/or regioselective deuterations of H-11αin 1-3 and both H-11αand H-11βin aconicarmisulfonine A(4);(d)TMSP-2,2,3,3-d4 promoted cleavage of the C-12-C-13 bond of 4 in D2 O;(e)dehydrogenation of 4 in pyridine-d5,and(f)Na2 SO3-assisted dehydrogenation and N-deethylation of songorine(5,a putative precursor of 1-4).Biogenetically,1 and 2 are correlated with 4,for which the same novel carbon skeleton is proposed to be derived from semipinacol rearrangements via migrations of C-13-C-16 and C-15-C-16 bonds of the napelline-type skeleton,respectively.Meanwhile,3 is a highly possible precursor or a concurrent product in the biosynthetic pathways of 1,2,and 4.In the acetic acid-induced mice writhing assay,at 1.0 mg/kg(i.p.),compounds 1,2,5,5 a,and 5 b exhibited analgesic effects against mice writhing.
文摘Abstract: Two new hetisine-type C20-diterpenoid alkaloids named spiraqine (1) and 6-hydroxylspiraqine (2), and four known alkaloids, namely spiredine (3), spiradine A (4), spiradine B (5), and spirasine V/VI (6), were isolated from Spiraea japonica L. f. var. fortunei(Planchon) Rehd. The structures of the alkaloids were elucidated using nuclear magnetic resonance analysis (1H-NMR, 13C-NMR, DEPT, HMQC, and HMBC) and mass spectrometry data.