Search

L-Tyrosine is degraded by Trichoderma hamatum to 3-(3'-isocy-anocyclopent-2-enylidene) propionic acid having Z-configuration about the exocyclic double bond, by fission of the aromatic ring and cyclization of the side chain of the amino acid.

Glycerol tri-dehydrocrepenynate (octadeca-9Z, 14Z-dien- 12-ynoate) is the most abundant (66 %) triacylglycerol in fruiting bodies of the Basidiomycete Craterellus cornucopioides . Glycerol trioleate and a linoleate-dioleate were also isolated from the fungus, in addition to minor unidentified triacylglycerols some of which contained further quantities of dehydrocrepenynic acid.

Three new esters of 2-(indol-3-yl)ethanol (tryptophol) containing the acyl residues of dehydrocrepenynic (octadeca-9Z,14Z-dien-12-ynoic), oleic and linoleic acids have been identified in fruiting bodies of the Basidiomycete Craterellus cornucopioides supplied with exogenous tryptophol. The esters were formed reversibly in high yields and are possible storage forms of auxin precursors which may be deposited in lipophilic cell compartments.

Polyacetylenes have been detected in sporophores of five Basidiomycete species. The new hydroxy-acids, HO·CH2·CH[graphic omitted]CH·[CC]2·CH2·CH2·CO2H and HO·CH2·CH[graphic omitted]CH·[CC]2·CH[graphic omitted]CH·CO2H, were found in Fistulina hepatica and isolated as the methyl esters.

The involvement of the crepenynate pathway and an ester of the metabolite HO·CH2·[CC]3·CH[graphic omitted]CH·CO2H in the biogenesis of NC·[CC]2·CH[graphic omitted]CH·CO2H (I) has been demonstrated in biosynthetic experiments with L. diemii cultures. The necessary ω-oxidation appears to be possible at both the C18 and the C10 stages. The carbon skeleton of (I) contains C(9)–C(16) of crepenynate.

Two acids have been isolated from cultures of the above fungus as the corresponding methyl esters; one is shown by X-ray crystallographic analysis to be methyl 3-(3-isocyano-6-oxabicyclo[3.1.0]hex-2-en-5-yl) acrylate (1), the other is probably methyl 3-(3-isocyanocyclopent-2-enylidine) propionate (2).

Extracts from the culture fluids of Lentinus lepideus, Leucopaxillus giganteus, Lyophyllum decastes, and Peniophora resinosa were found to contain Me[C[graphic omitted]C]3·CHCH·CH2OH as the major polyacetylene. The first two contained also the corresponding methyl ether, which was synthesised, and the third contained the corresponding aldehyde. The new polyacetylene (+)-Me[CC]3·CH[graphic omitted]CH·CH(OH) Et was isolated from the last culture.

The structure of the title compound was established by spectrometry and unambiguous synthesis of a simple transformation product.

From a culture of the fungus Marasmius alliaceus(Jacques ex Fr.) Fr. alliacolide, a new sesquiterpene hydroxy-epoxy-lactone, C15H22O4, has been isolated; its structure, which has been established by X-ray diffraction analysis, has a new sesquiterpene carbon skeleton.

The new polyacetylene HO·H2C·[CC]2·CH[graphic omitted]CH·CO2H and p-(methylamimo)benzaldehyde, not found previously as a fungal metabolite, have been detected together with known natural polyacetylenes in extracts from culture fluids of C. virgineus. Hygrophoraceae species have not been reported previously as polyacetylene producers. The synthesis of some of the polyacetylenes is described.

Examination of the above Dahlia species revealed the presence of 8 polyacetylenic compounds of which the C16 ene-diyn-ene alcohol (XXXII) and its acetate were new. In representatives of the main garden varieties 36 poly-MeCH[graphic omitted]CH·[CC]2·CH[graphic omitted]CH·CH(OH)·CH(OH)·CHCH2(XVIII), MeCH[graphic omitted]CH·[CC]2·[CH[graphic omitted]CH]2·CH(OH)·CH2·CH2OH (XXVIII), MeCH[graphic omitted]CH·[CC]2·[CH[graphic omitted]CH]2·[CH2]4·CH2·OH (XXXII), Me[CC]3·[CHCH]2·CH(OH)·[CH2]3·CHCH2(XXXVI), acetylenes were detected, including the new (XVIII), (XXVIII), and (XXXVI) and their acetates. Seasonal variations of the content were noted. The C17 alcohol (XXXVI) and the C16 alcohol (XXXII) were synthesised; the latter and the corresponding C14 compound by novel routes.

The structure and biosynthetic origin of the isonitrile-containing antibiotic (2) was established by experiments with [14C] and [13C]-tyrosine in cultures of Trichoderma hamatum(Bon.) Bain. aggr.

cis- and trans-1-Trimethylsilyl-pent-3-en-1-yne, -hex-3-en-1-yne, and -hept-3-en-1-yne have been prepared by fractional distillation of their cis–trans-mixtures and shown to provide a convenient route for the synthesis of the corresponding stereoisomeric terminal acetylenes.

The title compound was isolated from the esterified extract of Marasmiellus ramealis shake cultures and synthesized from the corresponding natural 3,7-bis(hydroxymethyl)benzoxepinone. In addition, several known metabolites, three new to M. remealis, were isolated from the culture fluid extract.

The sesquiterpenoids, alliacolide II (alliacol A)(2), 12-hydroxydehydroalliacolide (alliacol B)(3), 12-noralliacolide (5), 11- and 12-hydroxyalliacolide (6) and (7), respectively, and alliacide (8) have been isolated from Marasmius alliaceus and their structures established by a combination of their spectra and chemistry.

The (3S)-configuration has been assigned to EtCH(OH)·[CC]2H from Gymnopilus spectabilis and the (2R,7S)-and (2R)-configurations respectively to EtCH(OH)·[CC]2·CH(OH)·CH2·OH and EtCO·[CC]2·CH(OH)·CH2·OH from Clitocybe rhizophora cultures.

The new polyacetylenes (2S)-Me[CH2]2·[CC]3·CHCH·CH(OH)·CH2·OH, its glucoside and 3-phenyl-lactate and HO·CH2·CHCH·[CC]2·[CH2]2·CO2H, as well as the known acids HO·CH2·CHCH·[CC]2·[CH2]2·CO2H, HO·CH2·CHCH·[CC]2·[CH2]2·CO2H, and (2R)-PhCH2·CH(OH)·CO2H have been detected in extracts from the culture fluids of F. pallida. The natural C13 diol and its cis-isomer have been synthesised from 2,3-O-isopropylidene-D-glyceraldehyde.

The polyacetylene contents of one form of the species Dahlia coccinea Cav. var. coccinea and also of a horticultural form derived from the same species have been examined. The nineteen polyacetylenes detected comprised eight C13, eight C14, and three C17 compounds. Five of them were previously unknown; their isolation, characterisation, and structure determination are described. They are the C14 2,3-disbustituted tetrahydroprans CH3·[CC]3·CH[graphic omitted]CH·[graphic omitted] and CH3·CH[graphic omitted]CH·[CC]2·CH[graphic omitted]CH·[graphic omitted] (R = H or Ac), and the C17 acetate CH3·CH[graphic omitted]CH·[CC]2·[CH[graphic omitted]CH]2·CH(OAc)·[CH2]3·CHCH2.

Two crystalline compounds urospermal A and B, isolated from Urospermum dalechampii, are interconvertible in solution, and evidence is presented which indicates that they are conformers of the germacranolide aldehyde (II) or its mirror image.

Methyl crepenynate has been synthesised from non-3-yn-1-yl-triphenylphosphonium bromide (obtained from hept-1-yne via non-3-yn-1-ol and 1-bromonon-3-yne) and the C9 aldehyde-ester with butyl-lithiumin ether, and from it crepenynic acid was obtained by alkaline hydrolysis.

The diynol (–)-EtCH(OH)·[CC]2H has been found in Gymnopilus spectabilis, the triynol and triynoic acid Me[CC]3R (R = CH2·OH or CO2H) have been found in Psilocybe merdaria, Kuehneromyces mutabilis, Russula vesca, and Ramaria flava, and the acids H[CC]3·CH2·CH2·CO2H and HO2C·CH[graphic omitted]CH·[CC]2·CH2·CH2·CO2H have been obtained from Serpula lacrymans cultures. The Strophariaceae, Russulaceae, and Gomphaceae families have not been reported previously as polyacetylene producers.

Seven C10 polyacetylenes were isolated from Lactuca plumieriGren. and Godr. Dec-1-ene-4,6,8-triyn-3-one 1-hydroxydeca-4,6,8-triyn-3-one, (R)-deca-4,6,8-triyne-1,3-diol, and (R)-trans-1-(3-hydroxy-2-tetrahydro-furylidene)-hexa-2,4-diyne are new compounds and synthetic deca-4,6,8-triyn-1-ol is known. Dehydromatricarianol and its aldehyde are known natural products as also is heptadeca-8,10,16-triyne, now isolated from the garden lettuce, L. sativaL. These are the first polyacetylenes to be found in the Liguliflorae.

The new mono-ols RCH(OH)·[CC]2·CH[graphic omitted]CH·[graphic omitted] (R = Et or CHCH2) and the triols R[CC]2·CH[graphic omitted]CH·CH(OH)·[CH2]3·CH2·OH [R = EtCH(OH), CH2CH·CH(OH), or HO·CH2·CHCH] have been found in C. pyramidalis L. and C. medium L. (the Canterbury bell) and synthesised. A known mono-ol (III) and a known triol(VII) were also present.

The isolation and determination of the structure of the fungitoxic principle of the broad bean, Vicia faba L., is described. The natural material is the acetylenic keto-ester R[graphic omitted]·CH[graphic omitted]CH·CO2Me (R =cis-EtCH:CH·C⋮C·CO), contaminated with about 2% of the more saturated ketone (R = BuC⋮C·CO). In addition, the alcohol (R =cis-EtCH:CH·C⋮C·CHOH) was found in the shoot extract. These compounds, as well as the lower homologue (R =cis-MeCH:CH·C⋮C·CO), its trans-isomer, the aldehyde (R = OCH·C⋮C), the alcohol (R = HO·CH2·C⋮C), and the close thiophen analogue MeCH[graphic omitted]CH·C⋮C·CO·[graphic omitted]·CH[graphic omitted]CH·CO2Me were synthesised, and their fungitoxic properties were compared.

Hexa-2,4-diynal, octa-2,4-diynal, and octa-2,4,6-triynal (R[CC]n·CHO) dimerise in concentrated solution with evolution of carbon monoxide, to give products of the type R[CC]n– 1·CHC(CHO)·[CC]nR; above 100° even phenylpropargyl aldehyde reacts analogously. Both geometrical isomers of the ‘dimers’ were detected and characterised.

The esters R[CC]2·CH2CH[graphics omitted]CH·[CH2]7·CO2Me{R = Me[CH2]2, MeCC, cis- or trans-MeCHCH, trans-HO·CH2·CHCH, HO·CH2·CC, cis- or trans-MeO2C·CHCH, MeO2C·CC, (EtO)2CH, OHC, or, H2N·OC} were prepared from the Wittig salt Me3Si·CC·CH2·CH2·PPh3I–via ICC·CH2·CH[graphics omitted]CH·[CH2]7·CO2Me; several were specifically labelled [at C(9), C(17), and C(18)]. The Wittig salt offers a general route to 1-ene-4,6-diyne and more highly unsaturated skipped en-yne systems.

The isolation and determination of structure and absolute stereochemistry of the new triol MeCH[graphic omitted]CH·[CC]2·CH(OH)·CH(OH)·CH[graphic omitted]CH·[CH2]2·CH2·OH from Lobelia cardinalis L. and the hybrid Lobelia x vedariensis are described. The corresponding dihydroxy-aldehyde structure is suggested for a minor polyacetylene from the hybrid.

A modified Witting procedure makes possible the synthesis of 1-en-4-yne systems; ethynyl group protection with the trimethylsilyl group facilitates iodoacetylene formation for subsequent coupling reactions.

Labelled diethyl malonate, methyl oleate, methyl linoleate, and methyl crepenynate (CH3·[CH2]4·CC·CH2·CHCH·[CH2]7·CO2Me) were all incorporated into the triol CH3·CH2·CH(OH)·[CC]2·CH(OH)·CH2·OH by cultures of the fungus in the expected manner. Specifically labelled (14C and 3H) lachnophyllum ester (CH3·CH2·CH2·[CC]2·CHCH·CO2Me) has been synthesised and also shown to be a precursor of the triol.A new metabolite, CH3[graphic omitted]CH·[CC]2·CH2·CH2·OH, has been isolated.

The structure of the polyacetylenic keto-aldehyde {H2CCH·CO·[CC]2·CH2·CH[graphic omitted]CH·[CH2]7·CHO} has been determined. It is the first C18 polyacetylene to be isolated from a plant (Pastinaca sativa L.) of the main polyacetylene-producing families. Its occurrence almost certainly establishes the derivation of the C17 falcarinone and related compounds and is in harmony with Bu'Lock's hypothesis for the biogenesis of the natural acetylenes.

The new polyacetylenes HO2C·[CC]3·CH2·CH2·OH, cis- and trans-Me[CC]2·CHCH·CH2·CH2·OH, [Me[CC]3·CH2·CH2·OH, and (-)-Me[CC]3·CH(OH)·CH2·OH, as well as the known diol HO·CH2·CH2·[CC]2·CH2·CH2·OH, also new as a fungal metabolite, have been detected in extracts from the culture fluids of C. peronata and also synthesised.