Spermidine derivatives

For other fungal siderophores see neurosporin above, pistilarin (a spermidine derivative, Sect. 3.2) and rhizoferrin (a citrate siderophore, Sect. 4.4) siderophores... 

Pistillarin was first isolated from Clavariadelphus pistillaris and from several Ramaria spp. (Basidiomycetes) 334). Recently, it was found to be produced also by the marine fungus Penicillium bilaii 56). Like siderochrome II below it is a spermidine derivative substimted only at the terminal NHa-groups (A, iV °-di-(3,4-dihydroxy)benzoyl-spermidine). Its synthesis and that of siderochrome II was reported, their siderophore activity and their complexation with Fe (1 1 complexes) was investigated 102, 299). A derivative of pistillarin substituted at aU three amino functions has not been reported yet. 

The antifouling sponge metabolite pseudoceratidine (1245) was characterized from the Japanese Pseudoceratina purpurea (1253). This spermidine derivative has excellent larval settlement and metamorphosis inhibitory activity against the barnacle Balanus amphitrite (ED50 = 8.0 pig cm-3), and is the first example of an antifouling spermidine derivative. The four tauroacidins A (1246/1247) and B (1248/1249), with tyrosine kinase inhibitory activity, were isolated from the... 

Tsukamoto S, Kato H, Hirota H, Fusetani N (1996) Pseudoceratidine A New Antifouling Spermidine Derivative from the Marine Sponge Pseudoceratina purpurea. Tetrahedron Lett 37 1439... 

A revised structure for the catecholamide spermidine siderophore obtained from Paracoccus denitrificans has been proposed the new structure contains a centrally located oxazole ring (6).3 The soft coral Sinularia brongersmai contains two spermidine derivatives, i.e. (7) and its 10,11-dehydro-derivative [(lOi )], both of which show cytotoxic activity.4 The hypotensive principle of the root bark of Lycium chinense has been isolated as an amorphous alkaloid called kukoamine A.5 Acid hydrolysis of the alkaloid produced only spermine and dihydrocaffeic acid, which, in association with its n.m.r. spectrum, indicated the structure (8). Another hypotensive principle, ephedradine B (9), has been obtained from Ephedra roots.6... 

Tsukamoto, S., Kato, H., Hirota, H., and Fusetani, N., Pseudoceratidine a new antifouling spermidine derivative from the marine sponge Pseudoceratina purpurea, Tetrahedron Lett., 37, 1439, 1996. 

The Simple Open-Chain Spermidine Derivative of Natural Origin... 

Two cytotoxic spermidine derivatives were isolated as a mixture from the Pacific soft coral Sinularia brongersmai 5,12-dimethyl-1-dimethylamino-5,9-diazaheneicos-l l-en-10-one (35) and its 11,12-dihydroderivative 36 (ratio 9 1). By hydrogenation of the mixture, a single compound was obtained that corresponded by GC/MS analysis to the minor component of the original mixture. Hydrolysis followed by esterification of the hydrogenated product 36 afforded methyl 3-methyldodecanoate and N,N,N-tri-methylspermidine. The results of a Hofmann degradation of 36 confirmed the conclusion on mass spectral evidence that the primary amide nitrogen is bonded to the trimethylene chain of the unsymmetrical spermidine molecule (61). 

The inandenines are macrocyclic spermidine derivatives that have been isolated as ketones from Oncinot is species. The main alkaloids of the leaves of O. inandensis inandenin-12-one (53) and inandenin-13-one (54), exist as a mixture that has not yet been separated. Only by chemical degradation of the mixture to the ethylene acetal derivatives 55 and 56 it has been estab-... 

In the regiospecific total synthesis of codonocarpine (104), a partially protected spermidine derivative and a partially protected diphenyl ether... 

A spermidine derivative with two 4,5-dibromopyrrole-2-carbamyl units, pseudo-ceratidine (120), has been isolated from the sponge Pseudoceratina purpurea as an antifouling compound [145]. 

Fig. 33. Molecular pattern of spermidine derivative with the best plane of the SPIRO loop perpendicular to the plane of the figure...

Conformation polymorphism has been observed for a chiral s ivo-cis-ansa-bridged spermidine derivative of NPPh2(NPCl2)2 (121). ... 

Very few reactions of this type have been reported. The glutaric acid derivative (70) was esterified with A-hydroxysuccinimide and the resulting product (98) was used to selectively acylate the secondary nitrogen of various spermidine derivatives (Scheme 9) <82S689>. 

Comparison of the ORD-curves of tetrahydromeloscine (CXXXIV) and tetrahydroepimeloscine (3-epi-CXXXIV) with those of aspido-spermidine derivatives (Section II,A 59) leads to the probable absolute configurations shown. Biogenetically this group of alkaloids may be derived from tabersonine-like bases by way of an intermediate such as CXLI (1, 77). 

C2iH27N306, Mr 417.46, amoiphous solid. The fruit bodies of the giant club (Clavariadelphus pistillaris, Basidiomycetes) contains the bitter principle R, which is also responsible for the dark green color reaction of the toadstool with iron(lll) chloride solution. P. is a spermidine derivative and is also found in bitter species of coral fungi (Ramaria, Basidiomycetes). 

Curcubiturils are another class of host molecules that have been assembled into bilayer vesicles in water. Kim and coworkers synthesized an amphiphilic cucurbit[6]uril, which forms vesicles and forms host-guest complexes at the vesicle surface. It is possible to decorate the surface of the host vesicles with guest molecules. Exposure of cucurbituril vesicles to a fluorescent spermidine derivative led to fluorescent vesicles. Exposure of the cucurbituril vesicles to a-mannose-substituted spermidine led to vesicles coated with a-mannose, which binds specifically to the lectin concanavalin A. Concanavalin A does not bind when the vesicles are coated with a galactose spermidine... 

Finally, some workers suggest that still another type of oxidase, polyamine or spermine oxidase, is distinct from the above two types. Crude preparations of diamine oxidase attack spermine and spermidine derivatives and these compounds are usually considered as substrates of diamine oxidase 111). A partially purified diamine oxidase preparation did not attack spermine 18S). The compound was apparently not investigated with the highly piudfied preparation of Tabor 184). An adaptive amine oxidase from Neisseria perflava has been studied 185) which oxidatively d rades polyamines to diamines. Diamines and monoamines were not... 

Spermidine derivatives are known to have cytotoxic properties. Kazlauskas et al. 387) isolated two new N-methylated amides (742) and (743) from a species of Sinularia after the methanol extract had shown potent in vitro and in vivo activity against a human pathogenic bacterium Pseudomonas aeruginosa. The amides 742 and 743 which accounted for the antimicrobial activity were toxic and therefore unlikely to be of value as antibiotics. Some efforts have been made toward the synthesis of such spermidine derivatives derived from corals 387, 497). Three amides (744-746) different from those mentioned earher and derived from tyramine, have been reported as metabolites from Sinularia flexibilis 498). Structures of 744, 745, and 746 were deduced spectroscopically and that of 744 has been confirmed by synthesis. The amides (744-746) accounted for the cardiotonic activity which has been observed for the crude dichloromethane extract of S. flexibilis. 

Kazlauskas, R., Murphy, P.T., Ravi, B.N., Sanders, R.L., and Wells, R.J. (1982) Spermidine derivatives and 9-11-seco-steroids from a soft coral. Aust.J. Chem., 35, 69-75. 

Schmitz, P.J., Hollenbeak, K.H., and Prasad, R.S. (1979) Marine natural products cytotoxic spermidine derivatives from the soft coral Sinularia brongersmai. Tetrahedron Lett., 20, 3387-3390. 

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