Alkaloids from single skins of the Argentinian toad Melanophryniscus rubriventris (ANURA, BUFONIDAE): An unexpected variability in alkaloid profiles and a profusion of new structures

GC-MS analysis of single-skins of ten Melanophryniscus rubriventris toads (five collections of two toads each) captured during their breeding season in NW Argentina has revealed a total of 127 alkaloids of which 56 had not been previously detected in any frog or toad. Included among these new alkaloids are 23 new diastereomers of previously reported alkaloids. What is particularly distinguishing about the alkaloid profiles of these ten collections is the occurrence of many of the alkaloids, whether known or new to us, in only one of the ten skins sampled, despite two skins being obtained from each breeding site of the five populations. Many of the alkaloids are of classes known to have structures with branched-chains (e.g. pumiliotoxins and tricyclic structures) that are considered to derive from dietary mites. A large number of previously reported and new alkaloids are also of unclassified structures. Only a very few 3,5-disubstituted-indolizidine or -pyrrolizidine alkaloids are observed that have a straight-chain carbon skeleton and are likely derived from ant prey. The possible relationship of these collections made during the toad’s brief breeding episodes to sequestration of dietary arthropods and individual alkaloid profiles is discussed.Fil: Garraffo, H. Martin. Laboratorio de Bioorganic Chemistry; Estados UnidosFil: Andriamaharavo, Nirina R.. Laboratorio de Bioorganic Chemistry; Estados UnidosFil: Vaira, Marcos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina. Universidad Nacional de Jujuy. Facultad de Ingeniería; ArgentinaFil: Quiroga, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro de Investigaciones y Transferencia de Jujuy. Universidad Nacional de Jujuy. Centro de Investigaciones y Transferencia de Jujuy; ArgentinaFil: Heit, Cecilia Inés. Laboratorio de Análisis de Residuos y Trazas; ArgentinaFil: Spande, Thomas F.. Laboratorio de Bioorganic Chemistry; Estados Unido

62(P-39) Total Synthesis of Dart-Poison Frog Alkaloids 223A, 205B, 207I, 223I

A remarkably diverse array of biologically active alkaloids, for example, blockers of neuromuscular-type, ganglionic-type, and nicotinic receptor channels, occurs in amphibian skin, and over 500 alkaloids have been isolated to date. The structural diversity and pharmacological activity associated with these alkaloids have stimulated research in numerous synthetic groups. Among them, we achieved the first synthesis of the alkaloids 223A has been accomplished, the proposed structure has been revised, and the relative stereostructure of natural 223A was determined. We have demonstrated the first enantioselective total synthesis of the antipode of structurally unique alkaloid 205B, and the absolute stereochemistry of natural 205B has been determined to be 2aR, 5aR, 6S, 8S, 8aR. Furthermore, we achieved the chiral synthesis of quinolizidine 207I and its absolute stereochemistry was determined to be 1S, 4S, 10S by the GC-coinjection analysis of racemic compound and natural product. Finally, we also achieved the synthesis of both stereoisomers for the alkaloid 223I, and the determination of the ralative stereochemistry of natural 223I using GC-coinjection analysis of these isomers and natural product is now under investigations

sym-Homospermidine, a naturally occurring polyamine

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Individual and geographic variation of skin alkaloids in three swamp-forest species of Madagascan poison frogs (Mantella)

Seventy skins of three mantellid frog species from Madagascan swamp-forest habitats, Mantella aurantiaca, M. crocea, and M. milotympanum, were individually examined for skin alkaloids using GC/MS. These poison frogs were found to differ significantly in their alkaloid composition from species of Mantella originating from non-flooded rainforest in eastern Madagascar, which were examined in earlier work. Only 16 of the previously detected 106 alkaloids were represented among the 60 alkaloids from the swamp-forest frogs of the present study. We hypothesize this difference is related mainly to habitat but cannot exclude a phylogenetic component as the three swamp-forest species are a closely related monophyletic group. The paucity of alkaloids with unbranched-carbon skeletons (ant-derived) and the commonness of alkaloids with branched-carbon skeletons (mite-derived) indicate that oribatid mites are a major source of alkaloids in these species of mantellids. Furthermore, most of the alkaloids have an oxygen atom in their formulae. Differences in alkaloids were observed among species, populations of the same species, and habitats. In M. aurantiaca, small geographic distances among populations were associated with differences in alkaloid profiles, with a remote third site illustrating even greater differences. The present study and an earlier study of three other mantellid species suggest that oribatid mites, and not ants, are the major source of alkaloids in the species of mantellids examined thus far.Peer reviewe