Basidiomycetes polyacetylenes

Chemistry of the Higher Fungi. Part X. Further Polyacetylenic Derivatives of Decane from Various Basidiomycetes. T. Chem. Soc. [London]... 

Polyynes (polyacetylenes). Compounds with very diverse structures containing several C/C triple bonds are produced mainly by fungi (basidiomycete cultures) and plants of the families Asteraceae, Apiaceae, and Araliaceae. In addition to conjugated triple bonds the R often also contain C/C double bonds, allene units, thiophene and furan rings. On account of the close biosynthetic relationships between these compounds, the term R is used as a collective name even when only one C/C triple bond is present in the molecule. As result of the work of Bohimann, E. R. H. Jones, Sorensen, and others more than one thousand natural R are now known. The antibiotically active mycotnycin (C H, g02, Mr 198.22, mp. 75 °C) from basidiomycete cultures, dehydromatricaria ester (CiiHgO, Mr 172.18, mp. 105-106°C) from Asteraceae, and the thiarubrins may be mentioned as typical examples (see also ter-thienyls). 

The natural polyacetylenos were shown to have unbranehed chains of carbon atoms and a group of polyacetylenes from seed oils contained the Cig chain of stearic acid. It thus seemed possible that these substances were produced by modifications of the process of fatty acid synthesis. In conformity with this hypothesis, Bu Lock and Gregory found that nemotinic acid produced by a Basidiomycete in the presence of aeetate con-... 

Although all of the fungal polyacetylenes so far reported were isolated from mycelial cultures, they occur also in sporophores collected in the wild. In the course of a spectrophotometric survey of basidiomycete fruiting bodies, we have detected polyacetylenes in extracts of sporophores belonging to several genera of Basidiomycetes including Clitocyhe, Coprinus, Entoloma, Mycena, Hydnum and... 

The question has been raised of whether this organism really was an Actino-mycete, since there are no other reports of polyacetylenes from this group of organisms, and since mycomycin has recently been isolated in the laboratory of E. R. H. Jones from two Basidiomycete species (Bu Lock, 1964). Isolation of antiblastin", a polyacetylene identical with mycomycin, from a fungus characterized as a new species of fungi imperfecti" has also been reported (Nakamura et al, 1956). 

In general, the polyacetylenes known to be antibiotic were not recognized first as polyacetylenes, then tested for activity, but rather the reverse. Antibacterial activity was observed in a fungal or plant extract, and when the active principle was isolated and characterized, it proved to be a polyacetylene. Of the following examples, the first five were detected as the result of the earhest surveys of Basidiomycetes for antibiotic activity, (Wilkins and Harris, 1944 Robbins et al., 1945 Hervey, 1947), the last four as the result of isolated investigations of antibiotic principles from three different types of organisms. 

Drosophilin C (XVII) and drosophilin D (XVIII) (Jones et al., i960) represent another pair of polyacetylenes (Anchel, 1953b) detected and studied first as antibiotic principles of the Basidiomycete Drosophila subatrata (Kavanagh et al., 1952). 

The quadrifidins were detected as antibiotic compounds in cultures of the basidiomycete, Coprinus quadrifidus (Doery et al., 1951). The spectra of two of these compounds, published in the original paper, were characteristic of polyacetylenes. Because of this, the organism was later investigated again, and structures of four poly acetylenes isolated from it were reported (Jones and Stephenson, 1959). 

---