Structure, Biological Activity and Synthesis of Polyamine Analogues and Conjugates

Karigiannis, George; Papaioannou, Dionissios

doi:10.1002/(sici)1099-0690(200005)2000:10<1841::aid-ejoc1841>3.0.co;2-9

Cited by 119 publications

(36 citation statements)

References 211 publications

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“…[3] It is not surprising thus, that new and efficient methods for their synthesis as well as more sensitive and selective analytical methods for the identification and structural elucidation of new examples from natural sources are searched for.…”

Section: Introductionmentioning

confidence: 99%

Structure Elucidation of Polyamine Toxins in the Venom of the Spider Larinioides folium

Eichenberger¹,

Bigler²,

Bienz³

2007

Chimia

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The lyophilized venom of the spider Larinioides folium (Araneidae) was analyzed by highperformance liquid chromatography, coupled on-line to electrospray ionization mass spectrometry (HPLC-ESI-MS) and tandem mass spectrometry (HPLC-ESI-MS/MS), as well as UV-DAD analysis. In combination with amino acid analysis, high-resolution mass spectrometry and on-column H/D-exchange experiments, the structures of 41 new acylpolyamines contained in the complex venom of the spider L. folium were elucidated. Data interpretation in detail and the efficiency of this combined set of analytical method is exemplified by the structural elucidation of one of the toxins, namely of LF503a. Abstract: The lyophilized venom of the spider Larinioides folium (Araneidae) was analyzed by high-performance liquid chromatography, coupled on-line to electrospray ionization mass spectrometry (HPLC-ESI-MS) and tandem mass spectrometry (HPLC-ESI-MS/MS), as well as UV-DAD analysis. In combination with amino acid analysis, high-resolution mass spectrometry and on-column H/D-exchange experiments, the structures of 41 new acylpolyamines contained in the complex venom of the spider L. folium were elucidated. Data interpretation in detail and the efficiency of this combined set of analytical method is exemplified by the structural elucidation of one of the toxins, namely of LF503a.

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Section: Introductionmentioning

confidence: 99%

Structure Elucidation of Polyamine Toxins in the Venom of the Spider Larinioides folium

Eichenberger¹,

Bigler²,

Bienz³

2007

Chimia

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“…espite the prevalence of the biogenetic bases spermidine and spermine in nature and their widespread use as tools in biochemical research (1), little is known about the physiological properties of the small but structurally rather unique class of alkaloids incorporating these polyamines into their macrocyclic skeletons (2)(3)(4). This may be due, in part, to the difficulties in obtaining pure samples of these compounds from the natural sources † as well as to the fact that most syntheses described thus far provided only racemic material.…”

mentioning

confidence: 60%

Catalysis-based enantioselective total synthesis of the macrocyclic spermidine alkaloid isooncinotine

Scheiper

Glorius

Leitner

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

128

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A concise and efficient total synthesis of the spermidine alkaloid (؊)-isooncinotine (1) incorporating a 22-membered lactam ring is outlined. The approach is largely catalysis-based, involving a selective iron-catalyzed alkyl-aryl cross-coupling reaction of a difunctionalized pyridine substrate, a heterogeneous asymmetric hydrogenation step to set the chiral center of the target, and a highly integrated ring-closing metathesis͞hydrogenation sequence to forge the saturated macrocyclic edifice in a single operation. Despite the prevalence of the biogenetic bases spermidine and spermine in nature and their widespread use as tools in biochemical research (1), little is known about the physiological properties of the small but structurally rather unique class of alkaloids incorporating these polyamines into their macrocyclic skeletons (2-4). This may be due, in part, to the difficulties in obtaining pure samples of these compounds from the natural sources † as well as to the fact that most syntheses described thus far provided only racemic material. Prototype spermidine alkaloids are (Ϫ)-isooncinotine (1), (Ϫ)-oncinotine (2), (Ϫ)-neooncinotine (3), and oncinodin-12-one (4), which were isolated from the stem bark of Oncinotis nitida and Oncinotis tenuiloba (Apocynaceae) (5-7) and have been repeatedly targeted in the past (8-12) (Fig. 1). Only recently has one member of this series (i.e., compound 2) been made available in an optically active form through total synthesis by using a diastereoselective 1,3-dipolar cycloaddition for the formation of the stereogenic center at the junction of the piperidine and the macrocyclic ring (13).In pursuit of previous work in the field of polyamine alkaloids (14, 15), we were prompted to develop a complementary, practical, and potentially scaleable entry into this family of natural products, choosing the 22-membered macrolactam (Ϫ)-isooncinotine 1 as our initial target. The envisaged route, however, should not only provide material for further evaluation but also meet a set of stringent chemical criteria. Specifically, it is felt that contemporary organic chemistry must (i) prioritize catalysis-based bond formations, (ii) try to control absolute stereochemistry by asymmetric catalysis, and (iii) aim at high convergence combined with an overall ''economy of steps'' (16). Furthermore, the total synthesis of 1 should provide us with the possibility to scrutinize methodology developed in our laboratories. Outlined below is the successful reduction of this plan to practice. Materials and MethodsGeneral. All reactions were carried out under Ar in flame-dried glassware. The solvents used were purified by distillation over the drying agents indicated and were transferred under Ar: tetrahydrofuran (THF) (Na), CH 2 Cl 2 (P 4 O 10 ), MeCN, Et 3 N, pyridine, NMP, hexamethylphosphoramide (HMPA), tetramethylethylenediamine (CaH 2 ), dimethylformamide (DMF) (dibutyltin dilaurate͞Desmodur), MeOH, EtOH (Mg), and toluene (Na͞K). For flash chromatography, Merck silica gel 60 (230-400 mesh) was used. F...

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“…Following ammonolysis (control over the 1740 cm -1 band) with a double molar excess of 8 M solution of methylamine in ethanol gave the amide which was in turn converted to the target amine through the general reduction procedure. 4 was condensed with 1,3-dibromopropane in ethanol at 70 ˚C. The manner, the rate of mixing of the reagents and the isolation way were tuned up depending on what linear or cyclic target product is preferable.…”

Section: General Procedures For Amide Reductionmentioning

confidence: 99%

“…Biogenic short-chain polyamines, their analogs and derivatives are studied for many years. 4 Unfortunately, MPPA were not in focus of these investigations. There are several works only describing synthesis of MPPA with 3-6 nitrogen atoms 5 but the procedures are not universal and complicated with formation of amine mixtures.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of biomimetic polyamines

Annenkov¹,

Zelinskiy²,

Danilovtseva³

et al. 2009

Arkivoc

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Synthesis of methylated oligopropylamines by the stepwise repetition of reactions between methyl acrylate and amine, amidation and reduction of the resulting amide is reported. Longchain oligomers (average 15 nitrogen atoms) were obtained via condensation reactions utilising 1,3-dibromopropane. Three new acrylic monomers were prepared by reaction of oligopropylamines with acryloyl chloride. The synthesized amines and monomers are promising as model compounds for biosilicification reactions, as biologically active substances and as building blocks in organic and polymer chemistry.

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Structure, Biological Activity and Synthesis of Polyamine Analogues and Conjugates

Cited by 119 publications

References 211 publications

Structure Elucidation of Polyamine Toxins in the Venom of the Spider Larinioides folium

Structure Elucidation of Polyamine Toxins in the Venom of the Spider Larinioides folium

Catalysis-based enantioselective total synthesis of the macrocyclic spermidine alkaloid isooncinotine

Synthesis of biomimetic polyamines

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