Clitocybe acromelalga

Structurally rather complicated target molecules can be synthesized with the aid of thi-olate 1,6-addition reactions to acceptor-substituted dienes as well. For example, a richly functionalized proline derivative with a 2,4-pentadienal side chain was converted into the corresponding 6-phenylthio-3-hexen-2-one derivative by 1,6-addition of phenylthiolate, treatment of the adduct with methyl lithium and oxidation (equation 46)127. The product was transformed into acromelic acid A, the toxic principle of clitocybe acromelalga ichimura. Similarly, the 1,6-addition reaction of cesium triphenylmethylthiolate to methyl 2,4-pentadienoate served for the construction of the disulfide bridge of the macrobicyclic antitumor depsipeptide FR-901,228128. 

COjH >j C02H Japanese mushroom -Clitocybe acromelalga Acromeiic acids A-C -cytotoxic nonprotein amino acids 230... 

Toadstool -Clitocybe acromelalga Clithioneine - betaine from mushroom 217... 

Fukawatari, T., Suigimoto, E. and Shibata, K. (2001). Effect of feeding with a poisonous mushroom Clitocybe acromelalga on the metabolism of tryptophan-niacin in rats. Shokuhin Eiseigaku Zasshi, 42, 190-196. 

A number of kainoids have been isolated from the poisonous Japanese mushroom, Clitocybe acromelalga. Acromelic acid A 5 and acromelic acid B 6 were isolated from this source by Shirahama and co-workers6 in 1983, their structures being confirmed from total syntheses by Takano et al.7,8 and semisynthetic approaches by Shirahama.9-11 More recently, an additional three acromelates have been isolated acromelic acids C... 

Natural products that contain the imidazole nucleus have been found in such diverse sources as mushrooms and broiled fish. In the former, the fresh fruiting bodies of Clitocybe acromelalga contain the new amino-acid betaine clithioneine... 

Hashimoto, K., Konno, K., Shirahama, H., and Matsumoto, T., Synthesis of acromelic acid B, a toxic principle of Clitocybe acromelalga, Chem. Lett., 1399, 1986. 

Clitidine 5 -mononucleotide (115) was isolated from the Japanese toadstool Clitocybe acromelalga. Its structure was determined by UV, FABMS, elemental analysis, and lH and 31p... 

Clitidine was isolated among other nitrogen-containing principles from Clitocybe acromelalga, the toadstool long known in Japan as the cause of markedly increased hyperemia and hyperesthesia in fingers and toes. Pure... 

Ci.HuNjOfc, Mr 270.24, cryst., mp. 189-191 °C (monohydrate), [ajp -50.6° (HjO). A highly toxic pyridine nucleoside from the Japanese toadstool Dokusa-sako Clitocybe acromelalga, Basidiomycetes). The LDso (mouse) is less than 50 pg/kg. C. acts as an NAD analogue. The corresponding nucleotide is also present in the fungus. 

Alkaloids derived from glutamic acid, other than y-aminobutyric acid (GABA), include kainic acid isolated from Digenea simplex, domoic acid isolated from Chondria armata, acromelic acids isolated from Clitocybe acromelalga, ibotenic acid isolated from Amanita strobiliformis Amanita pantherina), and tricholomic acid isolated from Tricholoma musucaria, and are described in this chapter. 

Yamano K, Hashimoto K, Shirahama H. Novel neuroexcita-tory amino acid from Clitocybe acromelalga. Heterocycles 1992 34(3) 445 8. 

Yamano K, Shirahama H. New amino acids from Clitocybe acromelalga. Possible intermediates in the biogenesis of mushroom toxins, acromelic acids. Tetrahedron 1993 49(12) 2427-2436. 

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