Synthesis of Oncinotin‐11‐one, a Macrocyclic Polyamine Alkaloid from <i>Oncinotis tenuiloba</i>

Doll, Martin K.-H.; Guggisberg, Armin; Hesse, Manfred

doi:10.1002/hlca.19960790511

Cited by 10 publications

(6 citation statements)

References 32 publications

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“…One such recent example can be found in the synthesis of the branched alkaloid tenuilobine (14) by Hesse et al, [38] which involved ,N 9 -Boc 3 (67)-SPM, in moderate yields after chromatographic purification, [102d,104] from N 1 -Tfa-SPM (68) obtained as the major product in mixture with N 1 ,N 8 -Tfa 2 -SPM (54). These derivatives were shown to be suitable intermediates in the preparation of SPM-lipid conjugates.…”

Section: Methods For the Selective Functionalization Of Secondary Amimentioning

confidence: 98%

“…[35] These units can be either the same or combinations of HCA units. [36] Recently, N 4 -benzoylspermidine [37] and tenuilobine (14) [38] were isolated from the same source. Compound 14 is the first PA alkaloid containing both SPM and SPD, cross-conjugated through a long aliphatic chain.…”

Section: Linear Spermidine and Spermine Alkaloids From Plantsmentioning

confidence: 99%

“…Representative examples are the macrolactam SPD alkaloids oncinotines, such as the oncinotine (6), and inandenines, such as the inandenine-12-one (7), and the SPM alkaloids pithecolobines (8). [27,28] Other examples of macrocyclic SPD alkaloids are the loesenerines, such as the (R)-loesenerine (9), and myricoidine alkaloids, which contain a thirteen-membered lactam ring made up of SPD and part of a C 10 fatty acid.…”

Section: Macrocyclic Alkaloids From Plantsmentioning

confidence: 99%

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Structure, Biological Activity and Synthesis of Polyamine Analogues and Conjugates

Karigiannis

Papaioannou²

2000

Eur. J. Org. Chem.

119

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The structure and the biological significance of naturally occurring and synthetic polyamine analogues and conjugates are presented and the available methodologies for their synthesis are described. These methodologies involve either the selective functionalization of the amino functions, using suitable protecting groups or acylating agents, or fragment synthesis protocols. The latter employ suitable amino components and simple reactions, like Michael addition to α,β‐unsaturated nitriles, alkylation of amines and sulfonamides, reductive alkylation and acylation followed by reduction of the thus‐obtained amides, as key‐reactions, or azides as key‐intermediates, for the assembly of the polyamine skeleton. Syntheses performed in solution as well as in the solid phase are discussed.

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Section: Methods For the Selective Functionalization Of Secondary Amimentioning

confidence: 98%

Section: Linear Spermidine and Spermine Alkaloids From Plantsmentioning

confidence: 99%

Section: Macrocyclic Alkaloids From Plantsmentioning

confidence: 99%

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Structure, Biological Activity and Synthesis of Polyamine Analogues and Conjugates

Karigiannis

Papaioannou²

2000

Eur. J. Org. Chem.

119

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“…Deprotonation of the pyrazolo [3,4-b]pyridin-3-one 7 with sodium hydride and further nucleophilic substitution with dibromoethane allows the alkylation at the first position of heterocyclic system isolating compound 14 in pure form with 60% yield. The substitution of the derivative 14 with the saturated pyridodiazepine 21 in acetonitrile, in the presence of potassium carbonate and a catalytic amount of potassium iodide allow us to isolate the desired compound 15 in good yield (Scheme 8).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of new pyrazolo[3,4-b]pyridines and pyrazolo[1,5-a]pyrimidine and study of the pyrazolic nitrogen reactivity

Khouili¹,

Fadel²,

Hamri³

et al. 2011

Arkivoc

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“…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)(6)(7) and have been repeatedly targeted in the past (8)(9)(10)(11)(12) (Fig. 1).…”

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confidence: 99%

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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Synthesis of Oncinotin‐11‐one, a Macrocyclic Polyamine Alkaloid from Oncinotis tenuiloba

Cited by 10 publications

References 32 publications

Structure, Biological Activity and Synthesis of Polyamine Analogues and Conjugates

Structure, Biological Activity and Synthesis of Polyamine Analogues and Conjugates

Synthesis of new pyrazolo[3,4-b]pyridines and pyrazolo[1,5-a]pyrimidine and study of the pyrazolic nitrogen reactivity

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

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