Indolizidine and quinolizidine alkaloids

This review covers the isolation, structure determination, synthesis, chemical transformations and biological activity of indolizidine and quinolizidine alkaloids. Included in the review are the hydroxylated indolizidines lentiginosine, swainsonine, castanospermine and their analogues; alkaloids from animal sources, including arthropods and amphibians; alkaloids from the genera Polygonatum, Prosopis and Poranthera; phenanthroindolizidine and phenanthroquinolizidine alkaloids; Nuphar alkaloids; lupine alkaloids; and alkaloids from marine sources. 130 references are cited.     

Indolizidine and quinolizidine alkaloids

This review covers the isolation, structure determination, synthesis, chemical transformations and biological activity of indolizidine and quinolizidine alkaloids. Included in the review are the hydroxylated indolizidines lentiginosine, swainsonine, castanospermine and their analogues; alkaloids from animal sources, including ants, amphibians and beetles; indolizidine alkaloids from the genera Polygonatum, Prosopis and Elaeocarpus; indolizidine and phenanthroindolizidine alkaloids; alkylquinolizidine alkaloids, including myrtine, epimyrtine, plumerinine and Lycopodium metabolites; Lythraceae and Nuphar alkaloids; lupine alkaloids; and alkaloids from marine sources. 150 references are cited.     

Nature spermidine and spermine alkaloids: Occurrence and pharmacological effects

Spermidine and spermine are special polyamines in organisms, and produced in vivo by putrescine and S-adenosylmethionine catalyzed by a variety of enzymes. Spermidine and spermine possess multiple amino groups, and are closely related to cell division, growth and survival. Spermidine and spermine alkaloids are widely distributed in plants, bacteria and marine organisms, and can be divided into macrocyclic and open chain according to the skeletons. Spermidine and spermine alkaloids exhibited numerous pharmacological effects such as anti-inflammatory, antibiotics, anti-tumor, anti-Alzheimer and anti-virus. However, up to now, there are few systematic reviews on spermidine and spermine alkaloids. In this review, based on the number of atoms in the ring, we summarized the distributions and pharmacological effects of spermidine and spermine alkaloids. Spermidine and spermine alkaloids have special chemophenetic significances in the plant kingdom, especially the macrocyclic spermidine and spermine alkaloids. Spermidine alkaloids are much more abundant in nature than spermine alkaloids. The pharmacological activities of the open chain spermidine and spermine alkaloids are studied in depth. Polycyclic guanidine spermidine alkaloids, isolated from marine sponge, exhibit great potential in various cancer cells. However, pharmacological studies of macrocyclic spermidine and spermine alkaloids are scarce. Synthesis is an effective way to get more spermidine and spermine alkaloids and their analogues for further study.     

Role of plant alkaloids on human health: A review of biological activities

Alkaloids are plant secondary metabolite. They are well known nitrogen-containing natural bioactive compounds. Cutting edge research is going on alkaloids to unravel novel therapeutic approaches. Literature reveals that alkaloids contribute multiple biological activities and some alkaloids transform into active metabolites too. In this review, we have focused on marketed and experimental alkaloids. We have summarized sources and biological activities of reported alkaloids in past decades.     

Indolizidine and quinolizidine alkaloids

This review covers the isolation, structure determination, synthesis, chemical transformations and biological activity of indolizidine and quinolizidine alkaloids from microbial, plant and animal sources. Included in the review are the hydroxylated indolizidines lentiginosine, swainsonine, castanospermine and their analogues; alkaloids from animal sources, including ants, amphibians and beetles; ipalbidine, phenanthroindolizidines and related alkaloids; Lycopodium alkaloids; lupine alkaloids; and alkaloids from bacterial and marine sources. The literature from July 2002 to June 2003 is reviewed, and 174 references are cited.     

草乌中二萜类生物碱的电喷雾串联质谱研究

利用电喷雾质谱技术对传统中药草乌中的二萜类生物碱进行直接分析鉴定.通过实验数据并对比文献发现,草乌中含有单酯型、双酯型、三酯型和脂类等共4种类型生物碱,其中三酯型和脂类生物碱在草乌中为首次发现.由于这些生物碱的结构相似,在电喷雾串联质谱中碎裂方式相同,因此根据电喷雾串联质谱结果确定了这些生物碱的结构.     

16-O-去甲基去氧乌头碱在肠内细菌中的生物转化研究

采用人肠内细菌和乌头碱体外温孵的方法,探讨乌头碱的代谢产物16-O-去甲基去氧乌头碱在人肠内的生物转化。利用离子阱电喷雾串联质谱(ESIMS/MSn)方法直接分析16-O-去甲基去氧乌头碱的代谢产物。乌头类生物碱在ESI正离子模式条件下形成质子化分子[M H] 。16-O-去甲基去氧乌头碱可被人肠内细菌转化,通过脱乙酰基、脱苯甲酰基、脱甲基、脱羟基以及酯化反应产生新型的单酯型、双酯型和脂类生物碱等10余种代谢产物。双酯型生物碱具有较高的毒性,相对应的单酯型和脂类生物碱毒性较低。16-O-去甲基去氧乌头碱被肠内细菌转化为单酯型和脂类生物碱会使其毒性降低。     

Indolizidine and quinolizidine alkaloids

This review covers the isolation, structure determination, synthesis and biological activity of indolizidine and quinolizidine alkaloids from microbial, plant and animal sources. Included in the review are slaframine; hydroxylated indolizidines and their analogues; alkaloids from ants and amphibians; metabolites of the genera Prosopis, Streptomyces and Nuphar and the Lythraceae; phenanthroindolizidines and related alkaloids; lupin alkaloids; and alkaloids from sponges. tunicates and coccinellid beetles. The literature from July 2000 to June 2001 is reviewed, and 172 references are cited.     

Seven New Monoterpenoid Indole Alkaloids from Gelsemium elegans

Seven new indole alkaloids were isolated from the roots of Gelsemium elegans Benth. and their structures were determined by spectroscopic analysis and chemical transformation from known alkaloids. Kounaminal ( 1 ) is a new koumine‐type alkaloid that contains an unusual aminal moiety. Humantenoxenine ( 2 ) and 15‐hydroxyhumantenoxenine ( 3 ) are humantenine‐type alkaloids that contain a novel β‐amino‐α,β‐unsaturated ketone residue. The other four novel alkaloids are two gelsedilam‐related and two gelsenicine‐related alkaloids.     

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).     

Host-guest chemistry of alkaloids

Binding of alkaloids by different hosts (native and modified cyclodextrins, cucurbiturils, calixarenes, and metal complexes of porphyrin and Salphen-type ligands), as well as receptor properties of alkaloid based hosts are reviewed. With alkaloids as guests, the largest binding constants and most significant spectral changes, in particular strong fluorescence enhancements induced by complexation with isoquinoline alkaloids, are observed with cucurbituril hosts. Cyclodextrins are successfully employed for improvement of solubility and for chiral separation of alkaloids of different types. Receptor properties of native and modified cinchona and bisbenzylisoquinoline alkaloids have attracted considerable attention for development of chiral selectors for analysis and separation.     

A review on analytical methods for natural berberine alkaloids

Berberine alkaloids, a group of protoberberine alkaloids under the classification of isoquinoline alkaloids, include berberine, coptisine, palmatine, columbamine, dehydrocorydaline, jatrorrhizine, and epiberberine from natural sources. Studies have shown that berberine alkaloids have various pharmacological functions, such as antibacterial, antiviral, blood pressure‐lowering, hypoglycaemic, antiarrhythmia, and anticancer effects. Therefore, it is worthwhile to develop analytical methods to investigate the pharmacokinetics and activity mechanisms of berberine alkaloids and to study berberine alkaloids more comprehensively. Current analytical methods for berberine alkaloids include liquid chromatography, thin‐layer chromatography, ultraviolet spectroscopy, capillary electrophoresis, and gas chromatography. The most widely used detection method is mass spectrometry. In order to provide a systematic and comprehensive summary and to serve as a reference for the future pharmacokinetics studies and analysis of berberine alkaloids, analytical methods for natural berberine alkaloids that have been used in the past ten years are reviewed here.     

Selective separation of structure-related alkaloids in Rhizoma coptidis with "click" binaphthyl stationary phase and their structural elucidation with liquid chromatography-mass spectrometry

It is a new task to separate structure-related compounds into a fraction according to their structural characteristics in a complex traditional Chinese medicine (TCM). This method makes separation of the components of the sample simple and structural elucidation easy. In this study, selective separation of alkaloids in Rhizoma coptidis was realized on a "click" binaphthyl column possessing a planar conjugate structure. Three kinds of alkaloids, aporphine, tetrahydroprotoberberine and protoberberine in Rhizoma coptidis showed better retention than other compounds by virtue of π-π interactions with the stationary phase. Moreover, the "click" binaphthyl column could distinguish the aporphine and tetrahydroprotoberberine alkaloids possessing two benzene rings from the protoberberine alkaloids possessing three benzene rings. After separating on the "click" binaphthyl column, the fractions containing the alkaloids were collected and then analyzed with liquid chromatography-mass spectrometry (LC-MS). Totally, 23 alkaloids were identified, and among these alkaloids, three tetrahydroprotoberberine, two aporphine and seven protoberberine alkaloids were first found in Rhizoma coptidis. These newly found alkaloids are minor compounds, and they are always neglected without eliminating the interference of compounds in large amounts by pre-separation on the "click" binaphthyl column. The typical fragmentation pathways of each class of alkaloids were summarized to illustrate their structures. In the MS(2) spectrum, the loss of a molecule of dimethylamine ((CH(3))(2)NH) was observed as the characteristic loss of aporphine alkaloids. All the tetrahydroprotoberberine alkaloids would undergo the Retro-Diels-Alder (RDA) fragmentation reaction in the MS(2) fragmentation. For protoberberine alkaloids, different characteristic fragmentations were observed with different skeleton structures.     

The Lycopodium alkaloids

Lycopodium alkaloids are quinolizine, or pyridine and alpha-pyridone type alkaloids. Some Lycopodium alkaloids are potent inhibitors of acetylcholinesterase (AChE). Huperzine A (HupA) is reported to increase efficiency for learning and memory in animals, and it shows promise in the treatment of Alzheimer's disease (AD). 201 Lycopodium alkaloids from 54 species of Lycopodium (sensu lato) have been reported so far. This review is intended to to cover the chemical, pharmacological and clinical research on Lycopodium alkaloids reported in the literature from the spring of 1993 to August 2004. Structures of 81 new Lycopodium alkaloids are presented, classified and analyzed. The structural characters and biogenetic relationships of the four major Lycopodium alkaloid groups (lycopodine, lycodine, fawcettimine and miscellaneous) are discussed. Bioactivities of Lycopodium alkaloids, especially HupA, are summarized. In particular, the effect of HupA and other cholinesterase inhibitors (anti-AD drugs) on acetylcholine esterase (AChE) activity in the rat cortex and butylcholine esterase activity are compared. Structure-activity relationships and structure modifications of HupA and its analogs are described. Information on clinical trials with HupA and its derivative ZT-1 is presented. The state of HupA availability and recent advances in in vitro propagation of HupA producing plants are outlined. Finally, hypotheses about Lycopodium alkaloid biosynthetic pathways are discussed.     

Antineoplastic Alkaloids From Chinese Medicinal Plants and Their Analogs

The Chinese medicinal plant-derived antineoplastic alkaloids and their analogs are reviewed with emphasis on those discovered from the authors' laboratory. The active compounds include camptothecin, colchicine, ellipticine, harringtonine, Vinca alkaloids, indirubin, (-)-sophocarpine, lycobetaine, monocrotaline, d-tetrandrine, indicine N-oxide, maytansine, aporphine type alkaloids, palmatine, murrapanine, emarginatine alkaloids, and the alkaloids from Securinega virosa. The compounds are discussed briefly with the recent advances concerning their antitumor activity, structure-activity relationships and mechanisms of action.     

Indolizidine and quinolizidine alkaloids

This review covers the isolation, structure determination, synthesis, chemical transformations and biological activity of indolizidine and quinolizidine alkaloids from microbial, plant and animal sources. Included in the review are slaframine; the hydroxylated indolizidines lentiginosine, swainsonine, castanospermine and their analogues; alkaloids from amphibians and marine sources; plumerinine; ipalbidine, phenanthroindolizidines and related alkaloids; lasubine-II: and lupin alkaloids. The literature from July 2001 to June 2002 is reviewed, and 142 references are cited.     

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.     

Alkaloids ofLiriodendron tulipifera

The alkaloids of the tulip treeLiriodendron tulipifera L., family Magnoliaceae, are considered. More then 20 alkaloids have been isolated during different vegetation periods from various organs of the plant growing in Uzbekistan, and these have been assigned to the aporphine alkaloids and their dehydro, oxo, and 7-hydroxy derivatives; only two alkaloids proved to be derivatives of proaphorphine and of tetrahydroberberine. On the basis of the results of a comparative study of the NMR spectra of aporphines unsubstituted in ring D and some chemical transformations, the structure and configuration of the (R)-3-hydroxy-1,2-dimethoxyaporphine have been proposed for the new alkaloid lirinine. The absolute configurations, possible biogenetic interconnections, and mutual transitions of the alkaloids ofL. tylipifera that are derivatives of aporphine, oxoaporphine, and dehydroaporphine are discussed. A summery table is given which includes 41 alkaloids found in this plant.     

赣皖乌头生物碱的研究II. 江西兴国产赣皖乌头中其他生物碱的分离和鉴定

从江西兴国县赣皖乌头(Aconitum finetianum Hand-Mazz)根中分得五个二萜类生物碱,根据衍生物的制备、光谱分析及物理常数测定,证明其中两个为新生物碱,定名兴国乌头碱(finetianine)和1-去氢宋果灵(1-dehydrosongorine);其他三个为已知生物碱宋果灵(songorine)、诺密宁(nominine)和氨茴酰牛扁碱(anthranollycoctonine).     

Amaryllidaceae,sceletium, imidazole,oxazole, thiazole,peptide and miscellaneous alkaloids

This review covers alkaloids classified in the plant families Amaryallidaceae and Sceletium. In addition alkaloids possessing imidazole, oxazole and thiazole structures are listed followed by alkaloids possessing peptide linkages. Finally miscellaneous alkaloids include those compounds found naturally which cannot be classified into known groups; a relative Pandora's box. A total of 620 structures has been reviewed from 218 references found in the literature for the period July 1999 to June 2000.