Basidiomycetes sesquiterpenoids

Mori, K., Takaishi, H. Synthesis of mono- and sesquiterpenoids. XVI. Synthesis of (-)-pereniporins A and B, sesquiterpene antibiotics from a basidiomycete. Liebigs Ann. Chem. 1989, 939-943. 

Sesquiterpenoids related to eremophylane, synthesis of 80YGK783. Terpenoid metabolites of fungi and related basidiomycetes 81T2I99. 

Sesquiterpenoids are widespread metabolites of the Basidiomycetes. Lactarius species (milk or ink caps) are common Basidiomycetes that are found growing in woodlands. They are characterized by a latex which is exuded when the fruiting body is cut or broken. The colour and taste of the latex is of taxonomic significance. The latex of the edible species, Lactarius deliciosus, is at first carrot-coloured. On exposure to air it then darkens and turns a green-blue colour. The colour has been associated with the formation of an azulene, lac-taroviolin (5.55), which arises by the aerial oxidation of a dihydroazulene. 

Previously identified and new sesquiterpenoids were isolated from an unidentified fungus obtained from an Indo-Pacific sponge Jaspis aff. Johnstoni [103,104]. The mycelium gave coriolin B (76 extraction yield 3.8 mg/1) and dihydrocoriolin C (77 extraction yield 3.7 mg/1), which were previously reported from the terrestrial basidiomycete Coriolus consors. The broth gave chloriolin A (78 a white crystal extraction yield 4 mg/1), chloriolin B (79 a white solid extraction yield 3.5 mg/ml) and chloriolin C (80 a white solid extraction yield 0.6 mg/ml). The structure of these three new chlorinated compounds was determined by NMR experiments, synthetic transformations and X-ray crystallography. 

C15H18O4, Mr 262.31, powder, inp. 75-77°C, [a]u +42.7° (CHjCN). Biologically active sesquiterpenoid of the seco-sterpurene type (see sterpuranes) from mycelium cultures of Artomyces pyxidata (=Clavicorona pyxidata, Basidiomycetes). C. is an inhibitor of various RNA-dependent DNA-polymerases (reverse transcriptases) and acts against vesicular stomatitis viruses. IM. J. Antibiot. 45,29 (1992). - [CAS 139748-98-4]... 

C15H1JO4, Mr 262.31, oil, [a][>-79°. Sesquiterpenoid of the hirsutane type from cultures of the fungus Stereum complicatum (Basidiomycetes) see also hir-sutic acid. 

Sesquiterpenoids of the triquinane type produced by fungi. The key step in their biosynthesis is the cycliza-tion of humulene to hirsutene (C,5H24, Mr 204.36, oil) which is isolated from cultures of Coriolus con-sors (Basidiomycetes). Hirsutene has been synthesized by more than 20 different routes. Functionalized hir-sutanes such as complicatic acid, hirsutic acid, hyp-nophilin, pleurotellic acid, and the coriolins isolated from basirUomycete cultures all possess the absolute configuration shown for hirsutene. 

Illudanes. Sesquiterpenoids with the illudane skeleton occur in basidiomycetes and ferns ( pterosins). They are derived biosynthetically from humulene. Numerous derivatives of I. have been isolated from cultures of Omphalotus illudens (=Clitocybe illudens) and Lampteromyces japonicus, e.g., the toxic illudin M C15H20O3, Mr 248.32, cryst., mp. 130-131 °C, [ajp -126° (C2H5OH) and illudin S C15H20O4, Mr 264.32,... 

Sesquiterpenoids of the I. type are biosynthetically closely related with the sterpuranes with which they occur concomitantly in, e. g., cultures of Merulius tre-mellosus (Basidiomycetes) ( merulidial). Isolactarorufin C15H22O4, Mu 266.34, crystals, mp. 81 °C, [a][) +8.4° (C2H,0H)) is isolated ftom fruit bodies of the agaric Lactarius rufiis, sterepolide from cultures of the resupinate polypore Stereum purpureum. 

C18H20O5, Mr 316.35, yellow cryst., mp. 174-176 °C, [a]j> -187.1 ° (CHCI3). An antibacterially and cytotox-ically active sesquiterpenoid of the protoilludane type from mycelia cultures of Lentinellus omphalodes and L. ursinus (Basidiomycetes). The biosynthesis probably involves condensation of malonic acid with a pro-toilludane aldehyde ( Armillaria sesquiterpenoids). Lit. Z. Naturforsch. C 43, 177 (1988). - [CAS II52I9-90-4]... 

C,sH2202, Mr 234.34, oil, [aJo -h129.5 (CH3OH). A sesquiterpenoid from cultures of the agaric Lepista irina (Basidiomycetes). 

Sesquiterpenoids derived biosynthetically from hu-mulene and isolated from the fruit bodies and cultures of basidiomycetes, the best known examples are iso-velleral, marasmic acid, and stearoylvelutinal. Ma-rasmenes are sesquiterpenes with the drimane skeleton. 

Sesquiterpenes (sesquiterpenoids). A structurally highly diverse class of terpenoids with 15 carbon atoms skeleton derived biosynthetically from famesyl pyrophosphate (FPP) ( famesol, isoprene rule, ter-penes). More than 70 different ring systems are formed by enzyme-catalyzed cyclization of the linear parent structure these cyclic structures can be further modified by 1,2- and 1,3-hydride shifts, renewed cycliza-tions, hydroxylations, and other subsequent reactions. S. are widely distributed in plants, fiingi, and animals but are less common in bacteria. Specific biosynthetic routes are often characteristic for certain organisms. Thus, basidiomycetes preferentially use humulene as the basis for the syntheses of protoilludanes, illu-danes, lactaranes, hirsutanes, and related S. skeletons. Individual S. systems are also known for liverworts and marine organisms. In addition, liverworts often contain the optical antipodes of S. known from plants. 

Sesquiterpenoids of the drimane type from the agaric Lactarius uvidus (Basidiomycetes). U. A C15H24O3,... 

A comprehensive review of terpenoid metabolites of the Basidiomycetes has sections on the biosynthesis of these compounds. Many of the sesquiterpenoids found in these fungi can in theory be derived by various cyclizations of humulene. Conformational calculations on humulene have been made with a view to predicting the role of stable conformers in its biosynthetic reactions. 

---