Polyacetylene antibiotics

Identification of an Antibiotic Polyacetylene from Clitocybe diatreta as... 

Anchel, M. Some Naturally Occurring Antibiotic Polyacetylenes. Trans. 

Structure o Diatretyne 2, an Antibiotic Polyacetylenic Nitrile from... 

Bendz, G. Marasin, an antibiotic polyacetylene, isolated from the culture... 

Since very little in vivo testing has been carried out with polyacetylenic antibiotics, the categorical assumption that the group as a whole cannot be of therapeutic interest may not be justified. Despite the fact that some antibiotic polyacetylenes are toxic and that some cause dermatitis (Reisch, I965) Robbins et al., 1947), it is conceivable that non-toxic representatives of this class might... 

Anchel, M. Acetylenic compounds from fungi. J. Am. Chem. Soc. 74, 1588 (1952) Anchel, M. Identification of an antibiotic polyacetylene from Clitocyhe diatreta as a suberamic acid ene-diyne. J. Am. Chem. Soc. 75, 4621 (1953a). 

Anchel, M. Some naturally-occurring antibiotic polyacetylenes. Trans. N.Y. Acad. Sci., Ser. II, 16, 337 (1954). 

Anchel, M. Structure of diatretyne 2, an antibiotic polyacetylenic nitrile from Clitocyhe diatreta. Science 121, 607 (1955)-... 

Thompson and M. C. Whiting Research on Acetylenic Compounds. Part LIX. The Synthesis of Three Polyacetylenic Antibiotics. J. Chem. Soc. [London] 1958, 951. 

Bidens pilosa L. var. minor (Blume) Sherff. Sien Feng Cao (Bur marigold) (leaf) Polyacetylenes (it is phototoxic), phenytheptatriyne.50 Antibiotic, treat bug bites, diarrhea, snakebite. Bactericidal, fungicidal. 

Included in such compounds are the fatty acids, polyacetylenes, prostaglandins, macrolide antibiotics and many aromatic compounds, e.g. anthraquinones and tetracyclines. 

The first fungal polyacetylenes like mycomycin (33) and agrocybin (39) were detected and isolated on account of their antibiotic properties however, their comparative instability precluded any practical application. 

Several polyacetylenes have antibiotic properties and some are phytotoxic. Agrocybin (4.105), originally isolated from Agrocybe dura, is also formed by the fairy-ring fungus, Marasmius oreades, and it may be responsible for the death of grass. Their production as extracellular mycelial metabolites may thus facilitate the spread of the mycelium in a hostile environment. The dry-rot... 

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). 

In 1952 Anchel reported that a number of antibiotics produced by Basi-diomycetes were polyacetylenes . Compounds of this class had been known since 1935 to be produced by plants and those of the Compositae had been investigated systematically by Sorensen. The general chemistry of polyacetylenes was studied by Jones and his colleagues and by Bohlmann - . Many of these energy-rich compounds are extremely unstable and pol5nnerise rapidly in the solid state. However, they show characteristic ultraviolet absorption spectra which are useful in structural determinations. 

Some of the polyacetylene antibiotics are highly toxic and none has found clinical use. 

Outstanding properties Marine polyacetylenes constitute a very structurally diverse and useful class of compounds with Important biological activities such as antifungal, antibiotic, anticancer, antitumor, antl-HIV, anti-inflammatory, and antimicrobial properties. Legrave, N Elsebal, M F Mehirl, M Amade, P, Studies in Naturai Products Chemistry, Chapter 8, 251-95, Eisevier,2015. 

How about polyacetylenes There has been no systematic survey reported of the antibiotic properties of polyacetylenes, synthetic or natural. But of those which have been tested against a representative group of bacteria not all were active. Probably, one should not refer to mode of action of polyacetylenes as a class. It seems likely that antibiotic properties of polyacetylenes, as of many other compounds, depend on the special relationship of several groups in the molecule. This is well illustrated by two examples taken from the naturally-occurring polyacetylenes ... 

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. 

Biform5me 1 (XIV) (Jones et al., I963) was detected as an antibiotic principle C biformin ) in cultures of Polyporus biformis (Robbins et al., 1947), and later characterized as a polyacetylene (Anchel and Cohen, 1954 Anchel, 1956). 

Nemotin (XV) and nemotinic acid (XVI) (Bu Lock et al., 1955), isolated as antibiotic principles of a number of Poria species (Kavanagh et al., 1950b Anchel et al., 1950) were later recognized as polyacetylenes (Anchel, 1952). 

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). 

Bu Lock, J.D. Biosynthesis of polyacetylenes in fungi, p. 141. In J. F. Snell, Biosynthesis of antibiotics. New York Academic Press 1967. 

---