DOCSLIB.ORG

Isolation and Synthesis of Methyl Bovinate, an Unusual Pulvinic Acid Derivative from Suillus Bovinus (Basidiomycetes)

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Isolation and Synthesis of Methyl Bovinate, an Unusual Pulvinic Acid Derivative from Suillus Bovinus (Basidiomycetes) Isolation and Synthesis of Methyl Bovinate, an Unusual Pulvinic Acid Derivative from Suillus bovinus (Basidiomycetes) Helmut Besla, Andreas Bresinskya, Claus Kilpertb, Wolfgang Marschnerb, Helga M. Schmidtb, and Wolfgang Steglichc a Institut f¨ur Botanik der Universit¨at Regensburg, D-93040 Regensburg, Germany b Kekul´e-Institut f¨ur Organische Chemie und Biochemie der Universit¨at Bonn, Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany c Department Chemie und Biochemie, Ludwig-Maximilians-Universit¨at M¨unchen, Butenandtstraße 5 – 13, D-81377 M¨unchen, Germany Reprint requests to Prof. Dr. W. Steglich. E-mail: [email protected] Z. Naturforsch. 2008, 63b, 887 – 893; received February 1, 2008 Cultures and fruit bodies of Suillus bovinus produce the pulvinic acid derivative methyl bovinate (4), which contains an extra carbonyl group that bridges ring A of methyl variegatate with the hydroxy group at the central butenolide ring. This unprecedented structure was deduced from the spectroscopic data and confirmed by total synthesis via a grevillin intermediate. In this synthesis, the menthyl group was used for carboxyl protection. Key words: Suillus, Boletales, Pulvinic Acids, Mushroom Pigments, Synthesis Introduction Suillus bovinus (L.: Fr.) Roussel (Kuhr¨ohrling) is a common bolete found in sandy pine forests in au- tumn. The fruit bodies contain boviquinone-4 as the main pigment [1], in addition to smaller quantities of bovilactone-4,4 [2], concentrated in the pink mycelium at the base of the fruit bodies. Atromentin [1] and the characteristic Boletales pigments atromentic acid (1), xerocomic acid (2), variegatic acid (3), and variega- Fig. 1. Pulvinic acids from mycelial cultures of S. bovinus. torubin represent a second set of coloured metabolites found in S. bovinus [3, 4] (Fig. 1). These common pul- of the organic phase on a polyamide column with vinic acids are also produced in mycelial cultures [5], acetone as eluent yielded an orange-yellow pigment in addition to an orange pigment, methyl bovinate fraction, which was further purified by preparative 4 (4) [3], which can be detected on TLC plates by its TLC on silica gel. Methyl bovinate ( ) was ob- colour change to red-violet on exposure to gaseous am- tained pure after column chromatography on acety- monia. In this communication we report on the isola- lated polyamide followed by repeated chromatography tion, structural elucidation and synthesis of this unique on Sephadex LH-20. The compound was also detected fungal metabolite. in the methanol extract of the fruit bodies by analytical HPLC. Results and Discussion Structural elucidation Isolation Methyl bovinate was obtained as an orange pow- The new pigment was isolated from mycelial cul- der, which exhibited UV/Vis maxima at λmax = 206, tures of S. bovinus, grown on Moser B fluid medium 246, 270, and 408 nm. The high-resolution mass spec- for 25 d. The cultures were extracted with acidi- trum shows a strong molecular ion at m/z = 412.0434 fied acetone, and the concentrated extracts were par- corresponding to the molecular formula C20H12O10. titioned between water and EtOAc. Chromatography In the 1H NMR spectrum a methyl ester signal at 0932–0776 / 08 / 0700–0887 $ 06.00 c 2008 Verlag der Zeitschrift f¨ur Naturforschung, T¨ubingen · http://znaturforsch.com 888 H. Besl et al. · Methyl Bovinate Scheme 1. Attempted synthesis of methyl bovinate (4). Table 1. 1H-coupled 13C NMR spectrum of compound 4a. b c Position δc Multiplicity , J (Hz), coupling partner 1 124.0 d, 7.6 (5-H) 2 108.1 D, 164 (2-H) 3 154.2 dd, 7.6 (5-H), 2.4 (2-H) 4 148.2 dd, 6.4 (2-H), 2.4 (5-H) 5 115.5 D, 164 (5-H) 6 110.9 dd, 8.8 (2-H), 1.4 (5-H) 7 158.6 dd, 4.8 (5-H), 1.4 (2-H) 1 121.3 d, 9.0 (3-H) 2 116.4 Dd, 160 (2-H), 6.8 (6-H) Fig. 2a. Methyl bovinate (4) (pulvinic acid numbering). 3 145.6 ddd, 6.6 (5 -H), 3.8 (2 -H), 1.2 (6 -H) 4 148.1 ddd, 7.0 (2-H), 7.0 (6-H), 3.0 (5-H) 5 116.1 D, 162 (5-H) 6 121.9 Dd, 164 (6-H), 7.6 (2-H) 1 162.7d s 2 102.0 dd, 4.6 (2-H), 1.4 (5-H) 3 157.1d s 4 135.4d s 5 117.7 dd, 4.8 (2-H), 4.8 (6-H) 6 165.9 q, 3.8 (OMe) OMe 53.0 Q, 149 (OMe) a b 1 100.6 MHz, in [D6]DMSO; multiplets due to J(C,H) couplings are indicated by capital letters; 3J (C,H) and other couplings are 3J , 13 in small letters; c confirmed by selective 1H decoupling; d inter- Fig. 2b. Important H C couplings (Hz) in the CNMR spectrum of 4. changeable. The height of the singlet at δC = 135.4 is half of that at 157.1 ppm. show the corresponding signals in the range of 154 – δH = 3.94 is present in addition to two aromatic sin- 167 ppm [7]. glets at δH = 7.45 and 7.52 and typical signals for In order to confirm this structure, we set out to un- a 3,4-dihydroxyphenyl residue, matching those ob- dertake the total synthesis of methyl bovinate. served for ring C of variegatic acid (3) [6]. The 1H- Total synthesis coupled 13C NMR spectrum (Table 1) contains 20 sig- nals, which can be ascribed to 19 signals in the aro- Our first synthetic approach to methyl bovinate (4) matic region and that of a methoxy group (δC = 53.0). started from the known acetal 5, which is easily avail- An analysis of this spectrum, assisted by selective de- able in two steps from veratraldehyde [8] (Scheme 1). couplings, allowed us to propose the 5H-furo[3,4-c] Lithium-halogen exchange with n-butyllithium fol- benzopyran structure 4 for methyl bovinate (Fig. 2a). lowed by addition of dimethyl carbonate afforded Of special significance for this assignment are the methyl ester 6a, which was then converted into alde- 3 JH,C-couplings depicted in Fig. 2b. Unusual is the hyde 7a by acidic cleavage of the acetal group. Con- high-field position of the singlet at δc = 135.4, which densation of aldehyde 7a with pyrandione 8 [9] in must belong to one of the oxygen-carrying carbon acetic acid containing a catalytic amount of HCl gave atoms in the butenolide ring. Simple pulvinic acids grevillin carboxylic acid 9a in high yield. Clearly, the H. Besl et al. · Methyl Bovinate 889 Scheme 2. Synthesis of methyl bovinate (4). methyl ester group was not stable enough to survive arated on a silica gel column. The structural assign- the condensation conditions. Attempts to carry out this ment is based on the chemical shifts of the ortho pro- reaction under milder conditions (e. g., AcOH, ammo- tons at the 3,4-dimethoxyphenyl ring, those of iso- nium acetate, 20 ◦C) were unsuccessful, again yield- mer 13a appearing at lower field due to the deshield- ing the free acid 9a. The alcoholate-catalysed rear- ing effect of the neighbouring butenolide ring [6]. The rangement of the latter into the corresponding ter- desired diester 13b was obtained in 85 % yield, and phenylquinone [10], followed by treatment with min- we were pleased to note that treatment of diester lac- eral acid, proceeded with concomitant lactone forma- tone 13b with BBr3 in CH2Cl2 resulted in cleavage of tion and delivered quinone 10 in excellent yield. the menthyl ester [12] with concomitant lactone forma- In order to avoid the instability problems of the tion to give methyl bovinate (4), in every respect iden- methyl ester, we used the menthyl group for car- tical with the natural product. This confirmed the struc- boxyl protection. The desired (–)-menthyl ester 6b ture of this unusual fungal pulvinic acid derivative and could be easily prepared from bromo acetal 5 and demonstrated the advantageous use of a menthyl group (–)-menthyl chloroformate. After acidic cleavage of for carboxyl protection. Methyl bovinate (4) was ob- the acetal group, the resulting m-opianic acid men- tained from bromo acetal 5 in 7 steps with 11 % overall thyl ester 7b was condensed with pyrandione 8 to yield. yield grevillin carboxylic ester 9b (Scheme 2). We The co-occurrence of methyl bovinate (4) with var- were pleased to note that this reaction and the sub- iegatic acid (3) in fruit bodies and cultures of S. bovi- sequent methoxide-catalysed rearrangement into ter- nus points to a close biosynthetic relationship. Our at- phenylquinone 11 proceeded with retention of the tempts to introduce the extra carbonyl group by treat- ester group. Oxidative cleavage of dihydroxybenzo- ment of methyl variegatate with phosgene were unsuc- quinone 11 with Ac2O/DMSO according to Moore and cessful. 12 Wikholm [11] then afforded the dilactone in high Experimental Section yield. Treatment of the latter with dilute KOH in methanol General led to the formation of two regioisomeric monolac- Melting points (uncorrected): Reichert Thermovar hot tone diesters 13a and 13b, which could be easily sep- stage microscope. UV/Vis: Hewlett-Packard 8452 diode ar- 890 H. Besl et al. · Methyl Bovinate ray spectrophotometer. IR: Perkin-Elmer 1420 Ratio Record- coupled 13C NMR see Table 1. – MS (DI, 250 ◦C): m/z (%) = ing Infrared Spectrometer. Intensity of the bands: ss (very 412 (100) [M]+, 366 (50), 354 (60), 353 (85), 326 (35), 279 strong), s (strong), m (medium), and w (weak). NMR: (38), 235 (30), 120 (70), 44 (75). – HRMS: m/z = 412.0434 + Varian EM 390 with TMS as internal standard, Bruker (calcd.
Load more

Recommended publications
  • Covered in Phylloboletellus and Numerous Clamps in Boletellus Fibuliger
    PERSOONIA Published by the Rijksherbarium, Leiden Volume 11, Part 3, pp. 269-302 (1981) Notes on bolete taxonomy—III Rolf Singer Field Museum of Natural History, Chicago, U.S.A. have Contributions involving bolete taxonomy during the last ten years not only widened the knowledge and increased the number of species in the boletes and related lamellate and gastroid forms, but have also introduced a large number of of new data on characters useful for the generic and subgeneric taxonomy these is therefore timely to fungi,resulting, in part, in new taxonomical arrangements. It consider these new data with a view to integratingthem into an amended classifi- cation which, ifit pretends to be natural must take into account all observations of possible diagnostic value. It must also take into account all sufficiently described species from all phytogeographic regions. 1. Clamp connections Like any other character (including the spore print color), the presence or absence ofclamp connections in is neither in of the carpophores here nor other groups Basidiomycetes necessarily a generic or family character. This situation became very clear when occasional clamps were discovered in Phylloboletellus and numerous clamps in Boletellus fibuliger. Kiihner (1978-1980) rightly postulates that cytology and sexuality should be considered wherever at all possible. This, as he is well aware, is not feasible in most boletes, and we must be content to judgeclamp-occurrence per se, giving it importance wherever associated with other characters and within a well circumscribed and obviously homogeneous group such as Phlebopus, Paragyrodon, and Gyrodon. (Heinemann (1954) and Pegler & Young this is (1981) treat group on the family level.) Gyroporus, also clamp-bearing, considered close, but somewhat more removed than the other genera.
    [Show full text]
  • Secretion of Iron(III)-Reducing Metabolites During Protein Acquisition by the Ectomycorrhizal Fungus Paxillus Involutus
    microorganisms Article Secretion of Iron(III)-Reducing Metabolites during Protein Acquisition by the Ectomycorrhizal Fungus Paxillus involutus Firoz Shah 1,†, Markus Gressler 2, Susan Nehzati 1,3 , Michiel Op De Beeck 1 , Luigi Gentile 1,‡ , Dirk Hoffmeister 2 , Per Persson 4 and Anders Tunlid 1,* 1 Microbial Ecology Group, Department of Biology, Lund University, 223 62 Lund, Sweden; fi[email protected] (F.S.); [email protected] (S.N.); [email protected] (M.O.D.B.); [email protected] (L.G.) 2 Department of Pharmaceutical Microbiology at the Hans Knöll Institute, Friedrich-Schiller-Universität, 07747 Jena, Germany; [email protected] (M.G.); [email protected] (D.H.) 3 MAX IV Laboratory, Lund University, 221 00 Lund, Sweden 4 Centre for Environmental and Climate Research (CEC), Lund University, 223 62 Lund, Sweden; [email protected] * Correspondence: [email protected] † Current address: Department of Forest Biomaterials and Technology, Swedish University of Agricultural Sciences, 750 07 Umeå, Sweden. ‡ Current address: Department of Chemistry, University of Bari Aldo Moro, 70121 Bari, Italy. Abstract: The ectomycorrhizal fungus Paxillus involutus decomposes proteins using a two-step mechanism, including oxidation and proteolysis. Oxidation involves the action of extracellular hydroxyl radicals (•OH) generated by the Fenton reaction. This reaction requires the presence of iron(II). Here, we monitored the speciation of extracellular iron and the secretion of iron(III)-reducing metabolites during the decomposition of proteins by P. involutus. X-ray absorption spectroscopy showed that extracellular iron was mainly present as solid iron(III) phosphates and oxides.
    [Show full text]
  • Three Redundant Synthetases Secure Redox-Active Pigment Production in the Basidiomycete Paxillus Involutus
    Article Three Redundant Synthetases Secure Redox-Active Pigment Production in the Basidiomycete Paxillus involutus Graphical Abstract Authors Jana Braesel, Sebastian Go¨ tze, Firoz Shah, ..., Anders Tunlid, Pierre Stallforth, Dirk Hoffmeister Correspondence [email protected] In Brief Diarylcyclopentenones, produced by the symbiotic fungus Paxillus involutus, are redox-active metabolites involved in carbon cycling as they serve Fenton- based decomposition of lignocellulose in forest ecosystems. Braesel et al. show that the fungus uses three enzymes in parallel to secure the key step in diarylcyclopentenone biosynthesis. Highlights d Diarylcyclopentenone biosynthesis proceeds via atromentin as precursor d Atromentin biosynthesis in Paxillus involutus is a parallelized process d A thioesterase signature sequence indicative for quinone formation was identified d Quinone synthetases are amenable to engineering by domain swaps Braesel et al., 2015, Chemistry & Biology 22, 1325–1334 October 22, 2015 ª2015 Elsevier Ltd All rights reserved http://dx.doi.org/10.1016/j.chembiol.2015.08.016 Chemistry & Biology Article Three Redundant Synthetases Secure Redox-Active Pigment Production in the Basidiomycete Paxillus involutus Jana Braesel,1 Sebastian Go¨ tze,2 Firoz Shah,3 Daniel Heine,4 James Tauber,1 Christian Hertweck,4 Anders Tunlid,3 Pierre Stallforth,2 and Dirk Hoffmeister1,* 1Department of Pharmaceutical Microbiology, Hans Kno¨ ll Institute, Friedrich-Schiller-University Jena, Beutenbergstrasse 11a, 07745 Jena, Germany 2Junior Group Chemistry of Microbial Communication, Leibniz Institute for Natural Product Research and Infection Biology, Hans Kno¨ ll Institute, Beutenbergstrasse 11a, 07745 Jena, Germany 3Department of Biology, Lund University, So¨ lvegatan 37, 221 00 Lund, Sweden 4Department of Biomolecular Chemistry, Leibniz Institute for Natural Product Research and Infection Biology, Hans Kno¨ ll Institute, Beutenbergstrasse 11a, 07745 Jena, Germany *Correspondence: [email protected] http://dx.doi.org/10.1016/j.chembiol.2015.08.016 SUMMARY P.
    [Show full text]
  • Ro2c+O Meo2cgo Scheme 1
    J. CHEM. SOC. PERKIN TRANS. I 1984 1547 Dioxolanones as Synthetic Intermediates. Part 3.t Biomimetic Synthesis of Pulvinic Acids Robert Ramage" and Gareth J. Griffiths Department of Chemistry, University of Manchester Institute of Science and Technology, P. 0. Box 88, Sackvih'e Street, Manchester M60 70 D John N. A. Sweeney The Robert Robinson Laboratories, University of Liverpool, P.O. Box 147, Liverpool L69 3BX The reaction of the phosphorane (16) with methyl arylglyoxylates gives 5-(a-methoxycarbonyI- arylidene) -2,2-pentamethylene- 1,3-dioxolan-4-ones [ 5'(~-methoxycarbonylarylidene)cyclohexane- spiro-2'- (1',3'-dioxolan) -4'-ones] which have been treated with the lithium enolates of t-butyl phenylacetic esters to provide a biomimetic synthesis of pulvinic acids. By this method pulvinic acid (2), vulpinic acid (1), and the unsymmetrically substituted compounds, leprapinic acid (3),and xerocomic acid (4) have been prepared; the last named was obtained via an intermediate (28) in which the phenolic groups were protected as benzyl ethers. The pulvinic acids' have long been known as bright yellow and orange constituents of lichens. Vulpinic acid (1) was first isolated in 1831,2 and although pulvinic acid was not isolated from a natural source until 19523 its structure had been proposed by Spiegel in 1882 as a result of degradative studies on vulpinic acid.4 Other lichenal pulvinic acids, e.g. leprapinic acid (3), often contain methoxylated aromatic rings. More recently, pulvinic acids have been isolated from higher fungi of the closely related families Boletaceae and Gomphidaceae. These acids, e.g. xerocomic acid (4), differ from those of lichenal origin in that they are usually free acids rather than methyl esters, contain hydroxy rather than methoxy substituents, and are isolated in much lower yields.
    [Show full text]
  • Pigments of Higher Fungi: a Review
    Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102 Pigments of Higher Fungi: A Review Jan VELÍŠEK and Karel CEJPEK Department of Food Chemistry and Analysis, Faculty of Food and Biochemical Technology, Institute of Chemical Technology in Prague, Prague, Czech Republic Abstract Velíšek J., Cejpek K. (2011): Pigments of higher fungi – a review. Czech J. Food Sci., 29: 87–102. This review surveys the literature dealing with the structure of pigments produced by fungi of the phylum Basidiomycota and also covers their significant colourless precursors that are arranged according to their biochemical origin to the shikimate, polyketide and terpenoid derived compounds. The main groups of pigments and their leucoforms include simple benzoquinones, terphenylquinones, pulvinic acids, and derived products, anthraquinones, terpenoid quinones, benzotropolones, compounds of fatty acid origin and nitrogen-containing pigments (betalains and other alkaloids). Out of three orders proposed, the concern is only focused on the orders Agaricales and Boletales and the taxonomic groups (incertae sedis) Cantharellales, Hymenochaetales, Polyporales, Russulales, and Telephorales that cover most of the so called higher fungi often referred to as mushrooms. Included are only the European species that have generated scientific interest due to their attractive colours, taxonomic importance and distinct biological activity. Keywords: higher fungi; Basidiomycota; mushroom pigments; mushroom colour; pigment precursors Mushrooms inspired the cuisines of many cul- carotenoids and other terpenoids are widespread tures (notably Chinese, Japanese and European) only in some species of higher fungi. Many of the for centuries and many species were used in folk pigments of higher fungi are quinones or similar medicine for thousands of years.
    [Show full text]
  • Sendtnera = Vorm
    ZOBODAT - www.zobodat.at Zoologisch-Botanische Datenbank/Zoological-Botanical Database Digitale Literatur/Digital Literature Zeitschrift/Journal: Sendtnera = vorm. Mitt. Bot. Sammlung München Jahr/Year: 1999 Band/Volume: 6 Autor(en)/Author(s): Agerer Reinhard Artikel/Article: Never change a functionally successful principle: The evolution of Boletales s.l. (Hymenomycetes, Basidiomycota) as seen from below-ground features 5-91 © Biodiversity Heritage Library, http://www.biodiversitylibrary.org/; www.biologiezentrum.at Never change a functionally successful principle: The evolution of Boletales s.l. (Hymenomycetes, Basidiomycota) as seen from below-ground features* R. Agerer Summary: Agerer, R.: Never change a functionally successful principle: The evolution of Bo- - letales s.l. (Hymenomycetes, Basidiomycota) as seen from below-ground features. Sendtnera : 5-9 1 . 1 999. ISSN 0944-0 1 78. In the present study characteristics of substrate hyphae and of rhizomorphs have been applied as a completely new group of features to discern relationships of Boletales s.l. Rhizomorph structures have been shown to be very conservative. A so-called 'boletoid- rhizomorph type' is representative of Suillaceae, Rhizopogonaceae, Conio- phoraceae, Strobilomycetaceae, Paxillaceae, Pisolithaceae, Astraeaceae, Boletaceae and Sclerodermataceae. These rhizomorphs possess 'runner hyphae' where backward oriented ramifications grow towards the main hypha, after they have originated above the first simple septum or the first clamp of a side-branch. Frequently, these hyphae fork close to the main hypha into a distally and a proximally growing branch. The 'runner hypha' and additional ones enlarge and become vessel-like. Gomphidiaceae, Tapinellaceae and Truncocolumellaceae have different types of rhizomorphs. Conio- phoroineae and Tapinellineae are proposed as new suborders of Boletales s.l.
    [Show full text]
  • Conservation and Discreteness of the Atromentin Gene Cluster in Fungi
    bioRxiv preprint doi: https://doi.org/10.1101/2020.03.25.008516; this version posted March 26, 2020. The copyright holder for this preprint (which was not certified by peer review) is the author/funder. This article is a US Government work. It is not subject to copyright under 17 USC 105 and is also made available for use under a CC0 license. Conservation and discreteness of the atromentin gene cluster in fungi 1*# 2*# James P. Tauber ​ & John Hintze ​ ​ 1 Department​ for Materials and the Environment, BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87, 12205, Berlin, Germany. 2 Copenhagen Center for Glycomics, Department of Cellular and Molecular Medicine, Faculty of Health Sciences, University of Copenhagen, Blegdamsvej 3, DK-2200 Copenhagen N, Denmark. # equal​ authorship position * Correspondence:​ James P. Tauber at [email protected] , https://orcid.org/0000-0003-0351-9388 John Hintze at [email protected] , https://orcid.org/0000-0003-1420-7398 Key words: evolution, atromentin, natural product, fungi, regulation, transcription factor, promoter bioRxiv preprint doi: https://doi.org/10.1101/2020.03.25.008516; this version posted March 26, 2020. The copyright holder for this preprint (which was not certified by peer review) is the author/funder. This article is a US Government work. It is not subject to copyright under 17 USC 105 and is also made available for use under a CC0 license. Evolution of atromentin gene cluster Abstract The atromentin synthetase gene cluster is responsible for catalyzing the precursor pigment atromentin, which is further catalyzed into hundreds of different pigments that span different taxa in the Basidiomycota and is a distinguished feature of Boletales.
    [Show full text]
  • Dissimilar Pigment Regulation in Serpula Lacrymans and Paxillus Involutus During Inter- Kingdom Interactions
    Downloaded from orbit.dtu.dk on: Apr 02, 2019 Dissimilar pigment regulation in Serpula lacrymans and Paxillus involutus during inter- kingdom interactions. Tauber, James P.; Gallegos-Monterrosa, Ramses; Kovács, Ákos T.; Shelest, Ekaterina; Hoffmeister, Dirk Published in: Microbiology Link to article, DOI: 10.1099/mic.0.000582 Publication date: 2018 Document Version Peer reviewed version Link back to DTU Orbit Citation (APA): Tauber, J. P., Gallegos-Monterrosa, R., Kovács, Á. T., Shelest, E., & Hoffmeister, . D. (2018). Dissimilar pigment regulation in Serpula lacrymans and Paxillus involutus during inter-kingdom interactions. Microbiology, 164, 65- 77. DOI: 10.1099/mic.0.000582 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. Users may download and print one copy of any publication from the public portal for the purpose of private study or research. You may not further distribute the material or use it for any profit-making activity or commercial gain You may freely distribute the URL identifying the publication in the public portal If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. RESEARCH ARTICLE Tauber et al., Microbiology DOI 10.1099/mic.0.000582 Dissimilar pigment regulation in Serpula lacrymans and Paxillus involutus during inter-kingdom interactions James P. Tauber,1 Ramses Gallegos-Monterrosa,2 Ákos T. Kovacs, 2,3 Ekaterina Shelest4† and Dirk Hoffmeister1,* Abstract Production of basidiomycete atromentin-derived pigments like variegatic acid (pulvinic acid-type) and involutin (diarylcyclopentenone) from the brown-rotter Serpula lacrymans and the ectomycorrhiza-forming Paxillus involutus, respectively, is induced by complex nutrition, and in the case of S.
    [Show full text]
  • Bluing Components and Other Pigments of Boletes Stephen F
    Bluing Components and Other Pigments of Boletes Stephen F. Nelsen Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, WI 53706-1396 oletes, as well as many other fungi and lichens, contain compounds arising from enzyme controlled Bdimerization of p-hydroxyphenylpyruvic acid, which is derived by oxidation of the amino acid tyrosine, followed by either CO bond formation to produce grevillins such as grevillin A, or CC bond formation to produce hydroxylated terphenylquinone derivatives such as atromentin, as well as products of further reactions, including oxidative bond cleavage and rearrangement of atromentin with dehydration to dihydroxypulvinic acid (see Scheme 1), or further oxidation reactions. I discuss some pigments of boletes here. The material below on bolete pigments comes from the unrivaled review of mushroom pigments by Gill and Steglich (1987) which occupies an entire volume of the review series. Figure 1. Bluing reaction of Boletus luridus, which contains both variegatic and xerocomic acids (Scheme 2). (Newport State Park, Door Co., WI) The true structures of the compounds causing the bluing reaction of many members of Boletus and Suillus were not known until Edwards et al. (1968) showed the bluing to be caused by enzymatic oxidation of a more highly hydroxylated pulvinic acid derivative than the dihydroxy compound of Scheme 1, variegatic acid (in 1968 for B. erythropus, B. appendiculatus, S. varietatus and S. bovinus, later including Scheme 1. Outline of biosynthetic pathways to produce the bolete pigments B. pulverulentus, one of the fastest and atromentin, grevillin A, and pulvinic acid derivatives (Gill and Steglich, most intensely bluing species, and this 1987).
    [Show full text]
  • 14 Agaricomycetes
    14 Agaricomycetes 1 2 3 4 5 1 6 D.S. HIBBETT ,R.BAUER ,M.BINDER , A.J. GIACHINI ,K.HOSAKA ,A.JUSTO ,E.LARSSON , 7 8 1,9 1 6 10 11 K.H. LARSSON , J.D. LAWREY ,O.MIETTINEN , L.G. NAGY , R.H. NILSSON ,M.WEISS , R.G. THORN CONTENTS F. Hymenochaetales . ...................... 396 G. Polyporales . ...................... 397 I. Introduction ................................. 373 H. Thelephorales. ...................... 399 A. Higher-Level Relationships . ............ 374 I. Corticiales . ................................ 400 B. Taxonomic Characters and Ecological J. Jaapiales. ................................ 402 Diversity. ...................... 376 K. Gloeophyllales . ...................... 402 1. Septal Pore Ultrastructure . ........ 376 L. Russulales . ................................ 403 2. Fruiting Bodies. .................. 380 M. Agaricomycetidae . ...................... 405 3. Ecological Roles . .................. 383 1. Atheliales and Lepidostromatales . 406 C. Fossils and Molecular Clock Dating . 386 2. Amylocorticiales . .................. 406 II. Phylogenetic Diversity ...................... 387 3. Boletales . ............................ 407 A. Cantharellales. ...................... 387 4. Agaricales . ............................ 409 B. Sebacinales . ...................... 389 III. Conclusions.................................. 411 C. Auriculariales . ...................... 390 References. ............................ 412 D. Phallomycetidae . ...................... 391 1. Geastrales. ............................ 391 2. Phallales .
    [Show full text]
  • Two New Species of Chalciporus (Boletaceae, Boletales) from Tropical China
    Two new species of Chalciporus (Boletaceae, Boletales) from tropical China Chang Xu Hainan Medical University Zhi-Qun Liang Hainan University Hui-Jing Xie Hainan Medical University Shuai Jiang Hainan Medical University Xin-Hua Fu Hainan Medical University Nian-Kai Zeng ( [email protected] ) Hainan Medical University Research Article Keywords: New taxa, Molecular phylogeny, Morphology, Taxonomy Posted Date: April 28th, 2021 DOI: https://doi.org/10.21203/rs.3.rs-445603/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Page 1/19 Abstract Two new species of Chalciporus (Boletaceae, Boletales), viz. C. nigrofuscus and C. vulparius, are described based on morphological and molecular data. Detailed descriptions, color photographs of fresh basidiomata, and line drawings of microscopic features of the two new taxa are presented. In addition, a key to all known species of Chalciporus in China is provided. Introduction Chalciporus Bataille (Boletaceae, Boletales), typied by C. piperatus (Bull.) Bataille, was erected to accommodate species with peppery taste, reddish hymenophore, no-ornamental stipe, and smooth basidiospores (Moreno and García-Bona 1976; Pegler 1981, 1983; Baroni and Both 1991; Gómez 1996; Klofac and Krisai 2006; Halling et al. 2004). It is an early branching lineage in the Boletaceae (Nuhn et al. 2013; Wu et al. 2014). Among species of Chalciporus, the well-known C. piperatus was thought to be an ectomycorrhizal symbiont, nowadays it is believed to be a mycoparasite, colonizing Amanita muscaria (L.) Lam. ectomycorrhizae (Dickie et al. 2010, 2016). Although Chalciporus is a small genus, the species of this genus are distributed worldwide (Desjardin et al.
    [Show full text]
  • Chromapedic Acid, Pulvinic Acids and Acetophenone Derivatives from the Mushroom Leccinum Chromapes (Boletales)
    Chromapedic Acid, Pulvinic Acids and Acetophenone Derivatives from the Mushroom Leccinum chromapes (Boletales) Gertraud Gruber, Lydia Kerschensteiner and Wolfgang Steglich Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5 – 13 (Haus F), 81377 München, Germany Reprint requests to Prof. Dr. Wolfgang Steglich. Fax: +49-89-2180-77756. E-mail: [email protected] Z. Naturforsch. 2014, 69b, 432 – 438 / DOI: 10.5560/ZNB.2014-3307 Received December 2, 2013 Dedicated to the memory of the late Dr. Ryuji Marumoto The pigment responsible for the bright-yellow color of the stalk bases of Leccinum chromapes is methyl isoxerocomate, which is accompanied by lesser amounts of isoxerocomic acid and atromentic acid. In addition, 40-hydroxy- and 30,40-dihydroxyacetophenone, previously unreported as metabo- lites of Basidiomycetes, were isolated. The pink color of the cap skin is due to variegatorubin. This pigment is accompanied by chromapedic acid, a g-butenolide of biosynthetic interest representing a new dimerization mode of 4-hydroxyphenylpyruvic acid in Boletales. Key words: Boletales, Pulvinic Acids, Mushroom Pigments, Arylpyruvic Acid Dimers Introduction acid (2a)[2–4], atromentic acid ( 3)[5], and methyl isoxerocomate (2b)[2]. The use of EtOH instead of Leccinum chromapes (Frost) Singer (= Tylopilus MeOH in the extraction procedure yielded the same set chromapes (Frost) A. H. Sm. & Thiers), the ‘chrome- of compounds; thus, methyl ester 2b must be a genuine footed mushroom’, is a conspicuous bolete distributed constituent of the mushroom. in broad-leaved and coniferous woods in eastern North Compounds 1a, 1b, 2a, and 3 were identified by America, Japan, China, and East Siberia [1]. It can be their spectroscopic data (UV, IR, NMR, MS) and easily recognized by its pink cap, the pink scabrous HPLC comparison with authentic samples.
    [Show full text]