Alkaloids lupine

Feeding experiments utilizing C-, N-, and H-labeled cadaverine (44) and lysine (24) in l upinus augustifolius a source of the lupine alkaloids (—)-sparteine (50, R = H,H) and (+)-lupanine (50, R = O), have been reported which lend dramatic credence to the entire biosynthetic sequence for these and the related compounds discussed above (41). That is, the derivation of these bases is in concert with the expected cyclization from the favored aH-trans stereoisomer of the trimer expected on self-condensation of the 1-dehydropiperidine (45). 

It has become customary to call the principal members of this group the lupin alkaloids, but in view of their wide distribution in the Papilionaceae, a better title is that suggested above, since they appear to be the characteristic alkaloids of this leguminous sub-family. This is not the only type of alkaloid found in the Leguminosae other types occur, e.g., in Acacia (p. 631), Crotalaria (p. 601), Erythrina (p. 386), Mimosa (p. 4) and Pentaclethra (p. 776). 

Several lupin alkaloids have been derived from the unsaturated quinalozidine 433, that was obtained in the treatment of amine 431 with ortho-quinone 432. This quinone behaves as a model of topaquinone, the cofactor of copper-containing amine oxidases. The cyclization step involved a nucleophilic attack of the piperidine nitrogen of 431 onto a side-chain aldehyde function that is unmasked by the oxidative deamination. Quinolizine 433, when treated with dehydropiperidine, gave the oxime ether 434 that, on ozonolysis followed by reduction, afforded sparteine 10, presumably via the bis(iminium) system 435 (Scheme 102) <1996JOC5581>. 

In the course of biogenesis-type syntheses of lupin alkaloids, reduction of protected macrocyclic acyloin 50 (Scheme 15) has been found to be a second route to bicyclic aminoalcohol 14a (69JA7372). Another 11-membered ring compound, namely caprinolactam (51), on anodic oxidation in the presence of halide ions produces 6/7 bicyclic lactam 52 together with two isomeric 5/8 bicyclic lactams (87CJC2770). 

A remarkable number of insecticidal plants seem to have been recognized first as fish poisons. This group has received special scientific attention for example, the already mentioned rotenone and other rotenoids of Perris and Lonchocarpus species (3-6), the lupine alkaloids of Sophora species (13), and a saponin (medicagenic acid) from Medlcago sativa leaves ( ). 

Chemical ecology. It has been generally accepted that many of the so-called "secondary metabolites" play a role in the interrelationship of plant - plants, plant - microbes, and plant - herbivores (20-23). In a series of experiments we have sought to determine whether lupin alkaloids are important in an ecological context. 

Alkaloids are used as fertilizers for some crops. Mittex AG in Germany has developed a natural product, Lupinex, which contains quinolizidine alkaloids, minerals and carbohydrates. Lupinex has more than 9% N, 1% P and 2% K. The raw material for this natural product is a waste received from the lupin alkaloid remowing process, when the edible and non-edible components of food... 

Aniszewski, T. 1994. From iodine to enzyme A critical review of chemical and biological methods of lupine alkaloids analysis. Science of Legumes, 1 25-36. 

Cho, C. H., Chuang, C. Y. and Chen, C. F. 1986. Study of the antipyretic activity of matrine, a lupin alkaloid isolated from Sophora subprostata. Planta Medica, 343-345. 

Golebiewski, W. M. and Spenser, I. D. 1976. The biosynthesis of lupine alkaloids. A reexamination. Journal of American Chemical Society, 21 6726-6728. 

Cheek, P. R. and Kelly, J. D. 1989. Metabolism, Toxicity and Nutritional Implications of Quinolizidine (Lupin) Alkaloids. In Recent Advances of Research in Antinutritional Factors in Legume Seeds Animal Nutrition, Feed Technology, Analytical Methods. Proceedings of the First International Work shop on Antinutritional Factors ANF) in legume seeds. November 23-25, 1988 (Huisman, J., Poel, T. F. van der and Liener, I. E. eds.), pp. 189-201. Agricultural University, Wageningen. 

Cho, Y. D. and Martin, R. O. 1971. Resolution and unambiguous identification of microgram amounts of 22 lupin alkaloids by sequential use of thin-layer and gas-liquid chromatograhy and mass spectrometry. Analysis and Biochemistry, 44 49-57. 

Wiewiorowski, M. and Wolifiska-Mocydlarz, J. 1964. Structure of the new lupine alkaloid, dehydroalbine. Bulletin of the Polish Academy of Sciences. Chemistry, 12 213-222. 

Wysocka, W. and Brukwicki, T. 1988. Lupin alkaloids. I. Reinvestigation of the structure of N-methylalbine. Planta Medica, 54 522-523. 

Abdel-Halim, O. B., Sekine, T., Saito, K., Halim, A. F., Abdel-Fattah, H. and Mukaroshi, I. 1992. (+)-12a-hydroxylupanine, a lupine alkaloid from Lygos raetam. Phytochemistry, 31 3251-3253. 

Lupanine type alkaloids 88 Lupine alkaloids 165 Lupinidine 100... 

Quinolizidine alkaloids (lupine alkaloids) occur in the family Leguminosae, especially the subfamily Papilionaceae. They are also found in some species of other families such as Chenopodiaceae, Berberidaceae, Papaveraceae, Nymphaeaceae, Ranunculaceae, Scrophulariaceae, Solanaceae, Compositae, Rubiaceae, Monimiaceae, Ericaceae, and Adociidae. 

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