两种中药虎皮楠和交让木化学成分的研究

交让木(Daphniphyllum macropodum)和虎皮楠(Daphniphyllum angustifolium)属于虎皮楠科虎皮楠属,为小乔木.近年来,从虎皮楠属植物中分离得到一系列结构非常复杂的、独特的、生物活性多样的聚环生物碱[1,2],我们从交让木(D.macropodum)中分得7个此类生物碱,根据NMR和MS数据鉴定了3个化合物的结构,其中1个为新化合物.另外4个化合物的结构正在鉴定中.经文献查阅发现对该属植物非生物碱部分的研究很少,我们从虎皮楠)(D.angustifolium)非生物碱部位分得18个化合物,并根据NMR,UV,和MS等数据鉴定了它们的结构,其中7个为新化合物.新化合物的结构如下所示:     

虎皮楠生物碱研究进展

虎皮楠生物碱结构多变且具有复杂的多环骨架, 该类生物碱奇特的多环结构使其成为化学和生物合成研究的热点之一. 最近的关于虎皮楠生物碱的综述是由Kobayashi和Morita等于2003年报道的, 文章对1987到2002年间虎皮楠生物碱的研究进行了概括. 其后又有从11种虎皮楠植物中分离到的60多个新的虎皮楠生物碱报道, 其中三分之二是由中国学者从分布于中国的虎皮楠植物中分离得到. 这些新生物碱有的骨架类型已知, 有的骨架新颖. 故对这些新生物碱的结构分类、可能的生物合成途径和生物活性进行了综述. 对生物碱的分类基本按照以前提出的方法, 但增加了7种新的骨架类型. 对各种骨架的结构特点及在生物合成中的相互关系也进行了讨论.     

自苦木中分离得到两个新的β-咔巴啉生物碱——-苦木碱辛和苦木碱壬

自苦木科植物苦木的木质部分离得到四个生物碱,经UV,IR,NMR和MS分析和物理化学常数测定,确定其中两个为新的β-咔巴啉生物碱,分别命名为苦木碱辛和苦木碱壬.苦木碱辛的结构为1-甲酰基-4-甲氧基-β-咔巴啉(1),苦木碱壬的结构为1-甲氧丙酰基-β-咔巴啉(2).另外两个为已知生物碱1-乙烯基-4-甲氧基-β-咔巴啉(3)和3-甲基铁屎米-2,6-二酮(4)     

高脱氧三尖杉酯碱的合成及其差向异构体的分离鉴定

由2′-氧-6′-甲基-庚酰基-三尖杉碱(简称α-酮酰基三尖杉碱)(4)与α-溴代乙酸甲酯进行Reformatsky反应,得到一种新的三尖杉酯类生物碱——高脱氧三尖杉酯碱(5)及其差向异构体表高脱氧三尖杉酯碱(6)的混合物,产率67％.两者通过苦味酸盐分级结晶得纯品,它们的结构由IR、~1H NMR和MS推定.同法,由外消旋α-酮酰基三尖杉碱(±4)制得外消旋高脱氧三尖杉酯碱(±5)及外消旋表高脱氧三尖杉酯碱(±6),它们的IR、~1H NMR和MS分别与5和6一致.同时,还得到了少量副产物3-氧-(甲氧羰甲基)-三尖杉碱(7)及其外消旋体±7,它们的结构也由IR、~1H NMR和MS证明.     

喜树中的吲哚生物碱

从喜树(Camptetheca acuminata Decne)果中分到五个微量吲哚类生物碱, 其中两个为新生物碱, 分别为camptacumotint(1)和camptacumanine(2), 另外三个为已知生物碱naucleficine(3), angustoline(4)和新天然产物二氢异喹胺(dihydroisoquinamine, 5).     

展毛大渡乌头全草中的新二萜生物碱

从展毛大渡乌头(Aconitum franchetii var.villosulum)中分离得到11个C_(19)-二萜生物碱,经过HR-ESIMS,1D和2D NMR等波谱技术确定了它们的结构.其中一个为新的乌头碱型二萜生物碱,villosutine(1).其余10个为已知化合物,包含4个乌头碱型二萜生物碱、1个热解型二萜生物碱和5个大渡乌碱型二萜生物碱.     

中国乌头的研究 ⅩⅩⅡ.赣皖乌头生物碱的研究

从赣皖乌头(Aconitum finetianum Hand-Mazz)中又分得五个生物碱,其中三个为新的二萜类生物碱,分别命名为去氧刺乌头碱(deoxylappaconitine,3),赣乌新碱(neofinaconitine,4)和异刺乌头碱(isolappaconitine,5).经IR、MS、~1H和~(13)C NMR推定了它们的化学结构.另两个为已知生物碱ajacine(1)和inuline(2).     

几个新乌头碱型——二萜生物碱的13C核磁共振谱研究

本文报道云南药用乌头属植物中乌头碱型二萜生物碱乌头碱(aconitine,1),滇乌碱(yunaconitine,3),黄草乌碱甲(vilmorrianine A,5)、碱乙(vilmorrianine B,即karakoline,8)、碱丙(vilmorrianine C,7)、碱丁(vilmorrianine D,9)和鹤乌碱(scopaline,10)及3-乙酰乌头碱(2),3-乙酰滇乌碱(4)和3-乙酰黄草乌碱甲(6)的¹³C核磁共振谱。根据偏共振去偶及取代基加和律计算,并与类似物比较,对这些化合物各碳原子的共振讯号给予了指定,且进一步确定了新生物碱3,5,7,9的结构。对1,3,5,8及2,4,6中的羟基和乙酰基取代效应也作了分析,并通过对1,3,5及2,4,6的比较而修正了Pelletier对1中C₂和C₁₂化学位移的指定。还证明8中因C₁为α-OH而形成分子内氢键,使A环呈船式构型,所以A环上碳的化学位移与一般的椅式构型有显著差异。本文还报道了从鹤庆紫草乌(Aconitum episcopale Levl.)中分到的一新生物碱——鹤乌碱(scopaline)。根据红外光谱、质谱及¹H和¹³C核磁共振谱,确定其结构为10。     

白喉乌头中二萜生物碱及其拒食活性研究

从白喉乌头(Aconitum leucostomum Vorosch.)中分离得到13个二萜生物碱,采用HR-ESI-MS,1D NMR和2D NMR等波谱技术确定了它们的结构.其中一个为新的C_(18)二萜生物碱:刺乌宁,其余为已知化合物.同时考察了其中12个化合物对甜菜夜蛾3龄幼虫的拒食活性,结果表明化合物氨茴酰基牛扁碱和东乌头定的活性较好(EC_(50)1mg/cm~2),其次是N-acetylsepaconitine,赣乌碱和N-去乙酰高乌甲素(EC_(50)2 mg/cm~2).     

中国乌头的研究 XXII: 赣烷乌头生物碱的研究

从赣皖乌头(Aconitum finetianum Hand-Mazz)中又分得五个生物碱, 其中三个为新的二萜类生物碱, 分别命名为去氧刺乌头碱(deoxylappaconitine), 赣乌新碱(neofinaconitine)和异刺乌状碱(isolappaconitine), 经IR、MS、^1H和^1^3C NMR推定了它们的化学结构, 另两个为已知生物碱ajacine和inuline.     

Further Daphniphyllum Alkaloids from the Leaves of Daphniphyllum macropodum Miq.

Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds.     

Two New Daphniphyllum Alkaloids from Daphniphyllum calycinum

Two new daphniphyllum alkaloids named 2‐hydroxyyunnandaphnine D ( 1 ) and methyl 7‐hydroxyhomodaphniphyllate ( 2 ), together with eight known alkaloids, daphnioldhanin D, calyciphylline F, calyciphylline B, deoxycalyciphylline B, daphnicyclidin H, macropodumine C, 9,10‐epoxycalycine A, and yunnandaphnine A, were isolated from the stems and leaves of Daphniphyllum calycinum. Their structures and relative configurations were established on the basis of spectral evidence (including 2D‐NMR) and subsequently confirmed by a single‐crystal X‐ray crystallographic diffraction analysis.     

Alkaloids from the Fruits of Daphniphyllum macropodum

Three new alkaloids, N‐hydroxypaxdaphnine B ( 1 ), 21‐O‐acetylpaxdaphnine B ( 2 ), and methyl 17‐hydroxyhomodaphniphyllate ( 3 ), were isolated from the fresh fruits of Daphniphyllum macropodum, together with six known alkaloids. Their structures were established on the basis of extensive spectroscopic and mass‐spectrometric analyses in combination with chemical transformations.     

New Alkaloids from Daphniphyllum longeracemosum Rosenth.

Two new pentacyclic alkaloids, daphnilongertone ( 1 ) and 11‐hydroxydaphnigracine ( 2 ), together with the known congener dehydrodaphnigracine ( 3 ), were isolated from the fruits of Daphniphyllum longeracemosum. Their structures were elucidated spectroscopically. Compound 3 was isolated for the first time as a natural product.     

Alkaloids from Daphniphyllum longeracemosum

A new alkaloid, daphnilongeridine ( 1 ), together with six known alkaloids, daphmacropodine ( 2 ), daphmacrine ( 3 ), codaphniphylline ( 4 ), daphniyunnine A ( 5 ), daphniyunnine C ( 6 ), and daphniyunnine E ( 7 ), were isolated from the leaves and stems of Daphniphyllum longeracemosum. The so far elusive configuration at C(25) of daphmacropodine ( 2 ) was assigned on the basis of ROESY correlations.     

Alkaloids from the Twigs and Leaves of Daphniphyllum macropodum

Three new alkaloids, macrodumines A–C ( 1 – 3 , resp.), along with ten known analogs, were isolated from the twigs and leaves of Daphniphyllum macropodum. Their structures were elucidated on the basis of spectroscopic methods. The 11‐OH configuration of the known alkaloid hydroxydaphgraciline ( 4 ) was assigned as α for the first time by comparing the NMR data with those of macrodumine C ( 3 ).     

Further Alkaloids from the Fruits of Daphniphyllum longeracemosum

Three new Daphniphyllum alkaloids, daphlongeranines C–E ( 1 – 3 ), along with 13 known ones, were isolated from the fruits of Daphniphyllum longeracemosum. Their structures were elucidated on the basis of extensive spectroscopic analyses, especially 2D‐NMR experiments.     

Alkaloids from Fruits of Daphniphyllum oldhamii

Seventeen Daphniphyllum alkaloids, including two new pentacyclic alkaloids, yuzuric acid ( 1 ) and daphnezomic acid ( 2 ), and 15 known ones, were isolated from the fruits of Daphniphyllum oldhamii. The structures and configuration of the two new alkaloids were determined on the basis of spectroscopic methods, especially 2D NMR techniques.     

Two New Iridoid Alkaloids,Daphmacropodosidines A and B,from Daphniphyllum macropodum

Two new iridoid alkaloids, daphmacropodosidines A ( 1 ) and B ( 2 ), together with two known ones, daphcalycinosidine B and caldaphnidine F, were isolated from the fruits of Daphniphyllum maropodum. Their structures were established by spectral methods, especially 2D NMR spectra (¹H,¹H‐COSY, HMQC, HMBC, and NOESY), as well as chemical means.     

Two New Bis‐alkaloids from the Aerial Part of Piper flaviflorum

Two new bis‐alkaloids, flavifloramides A ( 1 ) and B ( 2 ), as well as two known alkaloids, N‐trans‐feruloyltyramine ( 3 ) and paprazine ( 4 ), were isolated from the aerial part of Piper flaviflorum. The structures of the new compounds were elucidated by spectroscopic analyses, including 2D‐NMR techniques.