Pigments of Higher Fungi: A · PDF filePigments of Higher Fungi: A Review ... only in some...

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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

VelíšekJ.,CejpekK.(2011): Pigments of higher fungi – a review.CzechJ.FoodSci., 29:87–102.

ThisreviewsurveystheliteraturedealingwiththestructureofpigmentsproducedbyfungiofthephylumBasidiomycotaandalsocoverstheirsignificantcolourlessprecursorsthatarearrangedaccordingtotheirbiochemicalorigintotheshikimate,polyketideandterpenoidderivedcompounds.Themaingroupsofpigmentsandtheirleucoformsincludesimplebenzoquinones,terphenylquinones,pulvinicacids,andderivedproducts,anthraquinones,terpenoidquinones,benzotropolones,compoundsoffattyacidoriginandnitrogen-containingpigments(betalainsandotheralkaloids).Outofthreeordersproposed,theconcernisonlyfocusedontheordersAgaricalesandBoletalesandthetaxonomicgroups(incertae sedis)Cantharellales,Hymenochaetales,Polyporales,Russulales,andTelephoralesthatcovermostofthesocalledhigherfungioftenreferredtoasmushrooms.IncludedareonlytheEuropeanspeciesthathavegeneratedscientificinterestduetotheirattractivecolours,taxonomicimportanceanddistinctbiologicalactivity.

Keywords:higherfungi;Basidiomycota;mushroompigments;mushroomcolour;pigmentprecursors

PartlysupportedbytheMinistryofEducation,YouthandSportsoftheCzechRepublic,ProjectNo.MSM6046137305.

Mushroomsinspiredthecuisinesofmanycul-tures(notablyChinese,JapaneseandEuropean)forcenturiesandmanyspecieswereusedinfolkmedicineforthousandsofyears.However, lit-tleisknownthatmushroomswereacommonlyusedtextiledyebeforetheinventionofsyntheticdyesbecauseofthevastrangeofvividandrichcoloursachievable(Mussak&Bechtold2009).Thechromophoresofmushroomdyescontainavarietyoffascinatingorganiccompounds.Theirpigmentationmayvarywiththeageandsomeundergodistinctivecolourchangesonbruising;therefore,thecoloursofmushroomsareoneoftheessentialfeaturesusedintheiridentification.Furthermore,thepigmentsofmushroomsmayprotecttheorganismfromUVdamageandbacte-rialattackorplayaroleasinsectattractants.

Mushroomsdonotcontainthepigmentsthatdominateinhigherplantcolours.Chlorophyllsandanthocyaninsarenotpresentinfungiatall;betalains,

carotenoidsandotherterpenoidsarewidespreadonlyinsomespeciesofhigherfungi.Manyofthepigmentsofhigherfungiarequinonesorsimilarconjugatedstructuresthataremostlyclassifiedac-cordingtotheperceivedbiosyntheticpathways,re-flectingtheirstructure,topigmentsderivedfrom(i)theshikimate(chorismate)pathway,(ii)theacetate-malonate(polyketide)pathway,(iii)themevalonate(terpenoid)pathway,and(iv)pigmentscontainingnitrogen.Severalreviewarticlescoveringthelitera-turepublishedfromitsinceptionduringthelatterhalfofthe19thcenturytotheendof2009havebeenalreadypublished(Gill&Steglich1987;Gill1994,1996,1999,2003;Hanson2008a,b;Räisänen2009;Zhou&Liu2010).

Theshikimatepathwayprovidesaroutetotheessentialaminoacidsphenylalanine,tyrosineandtryptophanviathecentralintermediatesshikimicandchorismicacids.Phenylalanineandtyrosineareprecursorsforawiderangeofcompoundsinclud-

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Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.

ingarylpyruvic,cinnamicandbenzoicacidsthatrepresentthebuildingblocksformanypigmentsofhigherfungi.Condensationoftwoarylpyruvicacidyieldsredtobrownterphenylquinonesandrelatedorangetoredgrevillins.Diarylcyclopentenones,responsibleforthecolourchangesinsomebruisedmushrooms,areformedbyringcontractionsofterphenylquinoneswhileoxidativecleavageofthehydroxyquinoneringinterphenylquinonesandrearrangementofthusformedintermediatesresultsinaseriesofyellowandorangelactonesknownaspulvinic(pulvic)acids.Theirdecarboxylationyieldstheyellowpulvinonesthatcanbeoxidisedandfur-thertransformedtoanumberofstructurallyrelatedproducts.Reductionofcinnamicacidsaffordsthecorrespondingalcoholsthatarethebuildingblocksofbenzotropolonepigments.Tyrosine,hydroxy-latedto3,4-dihydroxyphenylalanine(DOPA),istheprecursorofthered-violetbetacyaninsandtheorange-yellowbetaxanthins.Bothaminoacidsandtheirtransformationproductscanbeconvertedviaquinonesintotheheterogeneousdarkpigmentsmelaninsbytheenzymaticbrowningreactions(oxidationsandpolymerisations).Tryptophanistransformedtohydroxyanthranilicacidsthatbe-cometheprecursorofphenoxazinesandotherni-trogen-containingpigments.Benzoquinonescanbesynthesisedfromverydifferentstartingsubstancesandviadifferentbiochemicalpathways,e.g.usingbenzoicacidsproducedintheshikimatepathway.Terpenoidquinonesareformedbycombinationoftheshikimatepathwaywiththemevalonatepath-way.Thepolyketidepathwayyieldseitheraromaticketidesorfattyacids.Forthearomaticketides,thegrowingchainstabilisesbycyclizationreactionsandpartialreduction,whereasforfattyacids,thecarbonylgroupsofthechainarereducedbeforeattachmentofthenextC2group.Productsofthispathwayincludetetra-,hepta-,octa-andhigherketidesandcompoundsoffattyacidorigin.Fungicontainarangeofpigmentsofoctaketideorigin(e.g.anthraquinones)thatarebasedontheanthra-9,10-quinoneskeletonwithbothringssubstituted.Inmanycases,anthraquinonesarefoundinfungiasthecorrespondingcolourlessreducedforms

(anthranol,anthrone,anthrahydroquinone,andoxanthronederivatives)thatmayoccurintheformofvariousglycosides.Manynaturalanthraquinonesareoligomersformedbycouplingoftwoormoreanthraquinonemolecules.Theseoligomersfurtherdifferinthepointsthroughwhichmonomersareattachedandmayhavemorethanonepolymor-phicform(Velíšeket al.2007,2008;Velíšek&Cejpek2008).Styrylpyronesarebiosynthesisedbyacombinedshikimateandpolyketidepathway,whichotherwiseyieldsvariousterpenoidsinclud-ingcarotenoids.

Variouspigmentsandotherfungiconstituentsshowimportantbiologicalactivities(antioxidative,freeradicalscavenging,anticarcinogenic,immu-nomodulatory,antiviral,andantibacterial)thathavegeneratedintensiveresearchinterest(Steg-lich1981;Calìaet al.2003;Liu2006;MedicinalMushrooms2008;Schüffler&Anke2009).

ThetaxonomyofthekingdomFungi(thesubking-domDikarya)isinastateofconstantflux;therefore,themostrecent2007classificationadoptedbyacoalitionofmycologistswasused(Thorna et al.2007;MycoBank2010).Outofsevenphyla(divisions)proposed,theconcernofthisreviewonlydealswiththephylumBasidiomycota(“clubfungi”)1(subphy-lumAgaricomycotina,classAgaromycetes,subclassAgaromycetidae)thatcoversmostofthesocalled“high-erfungi”oftenreferredtoas“mushrooms”growinginEurope.Thereferredpigments,notrevieweduptonow,arearrangedaccordingtothemushroomorders.ManyotherpigmentswereidentifiedinfungiindigenoustoAustralasia.

1 Agaricales

ThegeneraAgaricusL.,LeucoagariusLocq.exSingerandMacrolepiotaSingeroftheAgaricaceae,includingthecommonmushroomA. bisporus (J.E.Lange)Imbach(nowcultivatedinatleast70coun-triesaroundtheworld),containtheglutamicacidderivedhydrazineagaritine(1)thatmaybeenzy-maticallyoxidisedattheC-4hydroxymethylgrouptothecorrespondingformylandcarboxylderiva-

1The clade containing Ascomycota and Basidiomycota is classified as subkingdom Dikarya. The phylum Ascomycota (“sac fungi”) covers some higher fungi (belonging to the subdivision Pezizomycotina, class Pezizomycetes, subclass Penzizomycodidae, order Pezizales), such as the true morel (Morchella Dill. ex Pers., Morchellaceae), the false morel (Gyromitra Fr., Discinaceae) and the truffle (Tuber P. Micheli ex F.H. Wigg., Tuberaceae). Their pigments have been stud-ied only sporadically; the black pigments of the black truffle T. melanosporum are polymeric allomelanins of polyketide origin (De Angelis et al. 1996).

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tives,whicharehydrolysedto4-(hydroxymethyl)-phenylhydrazineand4-carboxymethylbenzoicacid,respectively.4-(Hydroxymethyl)phenylhydrazineisoxidisedtothecorrespondingdiazoniumcation.Themetabolicfateofagaritinehasbeenlinkedwiththecarcinogenityofthemushroom(Waltonet al.2001).Theyellowpigmentcharacteristicoftheyellow-stainingA. xanthodermus Genev.andofsomeotherAgaricus species iscausedbyanotherazaquinonemetaboliteagaricone(2)thatformsbyoxidationofthecorrespondingleucophenolinthedamagedtissue.Theagaritineanaloguesderivedfrom4-aminophenolγ-glutamyl-4-hydroxybenzene(3)readilyoxidisetothecorrespondingquinoneviaγ-glutamyl-3,4-dihydroxybenzene.Thisquinonedecomposesto2-hydroxy-4-iminocyclohexa-2,5-dienone(4),whichimpartsapink-redcolourtosomeagarics(e.g.toA. bisporus)(Hanson2008a,b).

Thestrikingorange-redpigmentsofthecapofflyagaricAmanita muscaria(L.)Hook.(AmanitaPers.,Amanitaceae)areamixtureofthepurplebetacyaninmuscapurpurin(5),orangebetaxan-thinsmuscaurins(muscaaurins)I–VII(6 and7)

andyellowmuscaflavin(12).MuscaurinI(6)andmuscaurinII(7)arederivedfromunusualnonpro-teinaminoacidsibotenicacidandstizolobicacid,respectively,andarethemajoragaricpigments.PigmentsnamedmuscaurinsIII–VIIaremix-turesofpigmentsderivedfromcommonproteno-genousaminoacids.MuscaurinIIIisamixtureofvulgaxanthinI(8),knownas(S)-glutamine-beta-xanthin,miraxanthinIII(9),knownas(S)-asparticacid-betaxanthin,andabetaxanthinderivedfrom2-aminoadipicacid.MuscaurinIVisamixtureofvulgaxanthinIandmiraxanthinIII.MuscaurinVisamixtureofvulgaxanthinII(10),knownas(S)-glutamicacid-betaxanthin,indicaxanthin(11),knownas(S)-proline-betaxanthin,andbetaxan-thinsderivedfromvalineandleucine.MuscaurinVIisamixtureofvulgaxanthinIIandindicaxanthin.MuscaurinVIIisderivedfromhistidine(Muso1976;Li&Oberlies2005).

FlyagaricandmushroomsofthegenusHygrocybe(Fr.)P.Kumm.(Hygrophoraceae),e.g.H. conica (Schaeff.)P.Kumm.,commonlyknownasthewitch’shat,synthesisetheyellowpigmentmuscaflavin(12),

HO

NN

COOH

NH2

OH

H H

NNN

O

1. agaritine 2. agaricone

HO

N

O

NH2

COOH

H

O

NH

OH

3. glutamyl 4 hydroxybenzene 4. 2 hydroxy 4 iminocyclohexa 2,5 dienone

HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


O N

O

HOOC

NHOOC COOH

COO-

H

+

H

+N

O

OH

COO-

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO-

H

+

COOHHOOC N

N

COOH

COO-

5.muscapurpurin 6.muskaaurin I 7.muskaaurin II 8. vulgaxanthin I

H

+

COOHHOOC N

N

CONH2

COO-

H

+

COOHHOOC N

N COO-

COOH

H

+

COOHHOOC N

N COO-

N COOHHOOC

O

H

9.miraxanthin III 10. vulgaxanthin II 11. indicaxanthin 12.muscaflavin

N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O

2-

2 H+

13. hygroaurins (R = amino acid residue) 14. amavadin

O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3

15. fallacinol 16. (3R,3R ,M) flavomannin 6,6 di O methyl ether 17. (3R) atrochrysone, R = H(3R) torosachrysone, R = CH3

HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


O N

O

HOOC

NHOOC COOH

COO-

H

+

H

+N

O

OH

COO-

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO-

H

+

COOHHOOC N

N

COOH

COO-


H

+

COOHHOOC N

N

CONH2

COO-

H

+

COOHHOOC N

N COO-

COOH

H

+

COOHHOOC N

N COO-

N COOHHOOC

O

H


N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O

2-

2 H+


O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3


HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH

3. γ-glutamyl-4-hydroxybenzene 4. 2-hydroxy-4-iminocyclohexa-2,5-dienone

O N

O

HOOC

NHOOC COOH

COO–

H

+

H

+N

O

OH

COO–

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO–

H

+

COOHHOOC N

N

COOH

COO–

5. muscapurpurin 6. muskaaurin I 7. muskaaurin II 8. vulgaxanthin I

H

+

COOHHOOC N

N

CONH2

COO–

H

+

COOHHOOC N

N COO–

COOH

H

+

COOHHOOC N

N COO–

N COOHHOOC

O

H

9. miraxanthin III 10. vulgaxanthin II 11. indicaxanthin 12. muscaflavin

N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O2 H+


O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3

15. fallacinol 16. (3R,3R',M)-flavomannin-6,6'-di-O-methyl ether 17. (3R)-atrochrysone, R = H(3R)-torosachrysone, R = CH3

HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


O N

O

HOOC

NHOOC COOH

COO–

H

+

H

+N

O

OH

COO–

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO–

H

+

COOHHOOC N

N

COOH

COO–


H

+

COOHHOOC N

N

CONH2

COO–

H

+

COOHHOOC N

N COO–

COOH

H

+

COOHHOOC N

N COO–

N COOHHOOC

O

H


N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O2 H+


O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3


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derivedfromdihydroazepine,andstoreitinthecupskin.Analogouslytobetalamicacidinvolvedintheformationofbetalains,muscaflavincanspontane-ouslycondensewithaminoacids,undertheforma-tionofaldiminebonds,yieldingyellowhygroaurins(13)(Muso1976;Li&Oberlies2005).

TheunusuallyhighconcentrationofvanadiuminsomeAmanitaspeciesisascribedtotheforma-tionofamavadin(14),apalebluecomplex(1:2)ofvanadiumV4+with(2S,2´S)-N-hydroxyimino-2,2'-dipropionicacid, isolatedoriginally fromA. muscaria (Bayer&Kneifel1972).

Thegenus Cortinarius (Pers.)Gray(Cortina-riaceae)representsthelargestgenusofagarics,con-tainingabout1000differentspeciesinEuropeandfoundworldwidetogetherwiththecloselyrelatedgeneraDermocybe(Fr.)Wünsche(Cortinariaceae)andTricholoma (Fr.)Staude(Tricholomataceae). ArangeofanthraquinonesandbiogeneticallyrelatedmetaboliteshasbeenfoundinthesemushroomsprincipallyduetotheactivityinthestudyoftheAustralianCortinarius/Dermocybespecies.Thema-jordarkorangepigmentoftheEuropeantoadstoolC. cinnabarinusFr.isfallacinol(6-O-methoxycitre-orosein,15)(Gill&Steglich1987;Gill1994).SeveralspeciesofthegeneraCortinarius, Dermo-cybeandTricholoma,suchasC. cinnamomeoluteusP.D.OrtonandT. equestre (L.)P.Kumm.(triviallyknownasManonHorseback),produceabrightyellowdimericanthraquinoneflavomannin-6,6'-di-O-methylether(16).Thispigmentisbiosynthe-sisedby7,7'-couplingofthecorrespondinggreendihydroanthracenone(3R)-torosachrysone(17).InitshomochiralformitalsooccursintheEuropean

C. citrinusJ.E.LangeexP.D.OrtonandC. croceus (Schaeff.)Gray,whileinAustralianfungiitformsasamixtureof(3R,3R',M)-(16)and(3R,3R',P)-atropoi-somers.Thegreen(3R)-atrochrysone(17)occursinC. atrovirensKalchbr.andC. odoratus (M.M.Moser)M.M.Moser,(3S)-torosachrysone-8-O-methyletherinC. fulmineus (Fr.)Fr.,C. citrinus J.E.LangeexP.D.Orton,C. splendensR.Henry,T. equestre(L.)P.Kumm.andtheSulphurKnightT. sulphureum(Bull.)P.Kumm.(Gill&Steglich1987;Gill1994).Anumberofanthraquinonepigmentsformallyderivedfromtorosachrysoneandatrochrysonebycoupling(dimeric,trimericandtetramericoctaketides)havebeendescribed,mostlyinAustralianfungi belongingtothegenera Cortinarius,Dermocybeand,toalesserextent,Tricholoma (Gill&Morgan2001).

TheEuropeanmembersofthegenusCortinariuscharacteristicallycontainthexanthonedermoxan-thone(18)anditsmethylesterthatwerefoundinthestemoftheSurpriseWebcap C. semisanguineus (Fr.)Gill.ThesexanthonesareresponsibleforthebrightyellowfluorescenceunderUVlight(Gill1999).ThefruitingbodiesofseveralCortinariusspecies,suchastheVioletWebcapC. violaceus (L.)Gray,haveastrikinglydeepvioletcolourofthefruitingbodies,whichisascribestotheuniqueβ-DOPA-Fe3+complex[Fe3+L2(H2O2)]–or[Fe3+L4(H2O2)]2–,whereListhe(3R)-β-DOPAanionligand(19).Thesemushroomsconcentrateironbyasmuchas100-foldoverotherBasidiomycota(VonNussbaumet al.1998).Unusuallyhighcon-centrationsofironwerealsofoundintheVelvetBolete,Suillus variegatus(Sw.)Kuntze(Boletales)(Drbalet al.1975;Kalačet al.1989).

HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


O N

O

HOOC

NHOOC COOH

COO-

H

+

H

+N

O

OH

COO-

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO-

H

+

COOHHOOC N

N

COOH

COO-


H

+

COOHHOOC N

N

CONH2

COO-

H

+

COOHHOOC N

N COO-

COOH

H

+

COOHHOOC N

N COO-

N COOHHOOC

O

H


N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O

2-

2 H+


O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3


HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


O N

O

HOOC

NHOOC COOH

COO-

H

+

H

+N

O

OH

COO-

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO-

H

+

COOHHOOC N

N

COOH

COO-


H

+

COOHHOOC N

N

CONH2

COO-

H

+

COOHHOOC N

N COO-

COOH

H

+

COOHHOOC N

N COO-

N COOHHOOC

O

H


N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O

2-

2 H+


O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3


HO

NN

COOH

NH2

OH

H H

NNN

O


HO

N

O

NH2

COOH

H

O

NH

OH


O N

O

HOOC

NHOOC COOH

COO-

H

+

H

+N

O

OH

COO-

COOHHOOC N

N

H

+O

O

COOH

N

NHOOC COOH

COO-

H

+

COOHHOOC N

N

COOH

COO-


H

+

COOHHOOC N

N

CONH2

COO-

H

+

COOHHOOC N

N COO-

COOH

H

+

COOHHOOC N

N COO-

N COOHHOOC

O

H


N COOHHOOC

NR

COOH

H

+

H3CCH3

OO

N OO

CH3

CH3

OOO

N

V

O

O

2-

2 H+


O

O

H3CO

OH OH

OHO OH OH

OCH3

HO

CH3

OOHOH

H3COOH

CH3

OOHOH

ROOH

CH3


91


Scaurins(20)arethepolyenepigmentswithboundglutamicacidthatwereisolatedfromthefruitingbodiesofC. scaurus(Fr.)Fr.(Gill1998,2003).Alkaloidscontainingthecanthin-6-oneskeletonareproducedbysomeotherC.species.Theparentcompoundcanthin-6-one(21)occursinthebitter-tastingC. infractus(Pers.)Fr.togetherwiththeβ-carbolinederivativesinfractinAandB(22)(Gill1996).

Thebenzotropolonederivativeaurantricholone(23), isolatedfromthebrightorange-redcapsofTricholoma aurantium (Schaeff.)Ricken, iscloselyrelatedtothenaphthalenoidpulvinicacidbadioneAoccurringintheBoletalesmushrooms(seeChapter2). Itoccursnaturallyasametalchelate;thepredominantcounterioniscalcium(Klostermeyeret al.2000).MinorpigmentsaretheyellowaurantricholidesAandB(24).

Theyellow-brownstyrylpyronepigmentsbis-noryangoninandhispidin(25)arewidespreadamongfungioftheStrophariaceaefamily,generaGymnopilusP.Karst.,Hypholoma(Fr.)P.Kumm.

andPholiota(Fr.)P.Kumm.,wheretheyhaveaconsiderabletaxonomicsignificance(Gill1994).Hispidinisbiosynthesisedbytwodifferentmecha-nismsusingtheactivated4-hydroxy-6-methylpy-rone(acondensationproductofthreeactivatedacetates)andtheactivated3,4-dihydroxybenzoicacidorfromphenylalanineviaacinnamylderivativethatiscombinedwitheitheracetateormalonatethroughthepolyketidepathway.Therelatedopenchainβ-ketoester(26,R= COOCH3)wasisolatedsomeyearsagoastheBrickCapH. sublateritium(Schaeff.)Quél.pigment.Theyellowpigmenthispolon isthehydrolyticanddecarboxylationproductoftheopenchainβ-ketoester(26)(Gill1994).ItalsooccursinmushroomsoftheHy-menochaetaceaefamily,e.g.inseveralInonotus P.Karst.,OnniaP.KarstenandPhellinusQuél.species.(Lee&Yun2006)

Orange-yellowpolyenesof fattyacidorigin,dihydroxerulin,xerulinandxerulinicacid(27),arethepigmentsofOudemansiella melanotricha(Dörfelt)M.M.Moser (OudemansiellaSpeg.,

OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H

18. dermoxanthone 19. DOPA anion 20. scaurin A, R = Hscaurin B, R = OH

N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO

21. canthin 6 one 22. infractin A, R = H 23. aurantricholone 24. aurantricholide A, R = OHinfractin B, R = OH aurantricholide B, R = H

O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H

25. bisnoryangonin, R = H 26. hispolon, R = CH3 27. dihydroxerulin, R = CH2 CH2 CH3 28. stephanosporinhispidin, R = OH xerulin, R = CH=CH CH3

xerulinic acid, R = CH=CH COOH

N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H

29.mycearubin A 30.mycearubin B 31. sanguinone A, R = H 32. haematopodin, X = Osanguinone B, R = CH3 haematopodin B, X = NH

R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C

33. polyporic acid, R = H 34. leucomentin 2 35. flavomentin Aatromentin, R = OH

COO–

NH3+

O

O

–

–

19. β-DOPA anion

OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H

18. dermoxanthone 19. β-DOPA anion 20. scaurin A, R = Hscaurin B, R = OH

N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO

21. canthin-6-one 22. infractin A, R = H 23. aurantricholone 24. aurantricholide A, R = OHinfractin B, R = OH aurantricholide B, R = H

O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H

25. bisnoryangonin, R = H 26. hispolon, R = CH3 27. dihydroxerulin, R = CH2-CH2-CH3 28. stephanosporinhispidin, R = OH xerulin, R = CH=CH-CH3

xerulinic acid, R = CH=CH- COOH

N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H

29. mycearubin A 30. mycearubin B 31. sanguinone A, R = H 32. haematopodin, X = O sanguinone B, R = CH3 haematopodin B, X = NH

R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C

33. polyporic acid, R = H 34. leucomentin-2 35. flavomentin Aatromentin, R = OH

OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


92


Physalacriaceae)thatactasinhibitorsofcholes-terolbiosynthesis(Kuhntet al.1990).

Thecarrottruffle, Stephanospora caroticolor(Berk.)Pat.(StephanosporaPat.,Stephanospo-raceae),containsinitssubterraneantuber-likefruitingbodiesthepigmentstephanosporin(28).Thisunusualhydrazinederivativeisbiosynthesisedusing2-chloro-4-nitrophenolasthebuildingblock.Bothcompoundsoccurnaturallyastheirpotas-siumsaltsandareresponsibleforthebrightorangecolourofthemushroom(Langet al.2001).

ThepyrroloquinonealkaloidsisolatedfromMy- cena(Pers.)Roussel(Mycenaceae)speciesincludetheredpigmentsmycearubinA(29),mycearubinB(30)andrelatedcompoundsfromthefruitingbod-iesofM. rosea(Schumach.)Gramberg(Peters&Spiteller2007a)andtheBleedingFairyHelmet M. haematopus (Pers.)P.Kumm.Thebluesan-guinonesAandB(31)wereisolatedfromM. san-guinolenta(Alb.&Schwein.)P.Kumm.(Peters&Spiteller2007b)andredhaematopodinsfromthefragilereddish-brownstemsof M. haematopus(Hopmann&Steglich2006;Peterset al.2008).Thesealkaloidsareexemplifiedbytheminorpigmenthaematopodin(32),abreakdownproductofthelabileredhaematopodinB(32),whichisthemainpigment

ofthemushroomdecomposingundertheinfluenceofairandlight(Hopmann&Steglich2006).

2 Boletales

MushroomsoftheorderBoletalesarecharac-terisedbyadiversityofcoloursmainlyderivedfromterphenylquinonesandpulvinicacids.Ter-phenylquinones,exemplifiedbypolyporicacid(33)andatromentin(33),aremainlyproducedbywood-rottinghigherfungioftheorderPolyporalesgrowingonvariousdeciduoustreesbutinotherhigherfungi,suchasintheBoletalesfungi,theyonlyappearsporadically.However,atromentinistheirkeyintermediateformanyconversionsleadingtomorehighlyhydroxylatedterphenyl-quinones,hydroxypulvinicacids,cyclopentenonesandrelatedcompounds.Intheintactfruitbodies,atromentinoccursintheformofitscolourlessprecursorsleucomentins.

Leucoderivativeofatromentinesterifiedwith(2Z,4S,5S)-4,5-epoxyhex-2-enoicacidfromthelignicolousfungiTapinella atrotomentosa (Batsch)Šutara(TapinellaE.-J.Gilbert,Tapinellaceae)spo-rophoreisleucomentin-2(34)(Gill&Steglich1987;Gill1994;Liu2006;Hanson2008b).This

OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


OO

OOH

H3CO

OHOOC

COO-

NH3+

O

O

-

-

HO

RN

O

COOH

COOHH

H


N

O

N

COOCH3

R

H

O

O OHOHHO

HO

O

OO

OH O

OHO

RO


O

HO

RO

OH

HO

HOR

OOH

R

O

O

NN

O

COOH

OH

NO2

Cl

H

H



N

COOH

OO

NH2

NH N

NH2

NO

COOH

N

COOH

OO

HNNH

N

N

NHHN

R

H

HOOC

ON O

N

X

OH

H


R

R

O

O

OH

HO

OH

OO

OH

H3CO

O

H3C

O

O

OH

HO

O

OO

O

O

O

OCH3

OH3C


93


compoundandleucomentin-3,-4,-5and-6werefoundinanumberofotherfungi.MushroomsofthegenusTapinellaalsoproducesmallamountsoforange-yellowflavomentinsA-Dandvioletspiro-mentinsA-D(spiromentinsE-J,derivativesofben-zene-1,2,4,5-tetraol,arecolourless)derivedfromatromentin.Theflavomentinsconstitutediestersandmonoestersofatromentinwith(2Z,4S,5S)-4,5-epoxyhex-2-enoicand(2Z,4E)-hexa-2,4-dienoicacids.Thespiromentinspossessauniquespirostructure inwhicha4,5-dihydroxybenzo-1,2-quinoneislinkedtoalactoneacetalunit(Beslet al.1989).FlavomentinA(35)andspiromentinA(36)exemplifythesemetabolites.

Simpleoxidationproductsofterphenylquinonesunderthepreservationofthecentralquinoneringincludecycloleucomelone(37)andcyclova-riegatin(37),whichistheprecursorofthevioletthelephoricacid(38).CycloleucomeloneoccursinthefruitingbodiesofBoletopsis leucomelaena(Pers.)Fayod(BoletopsisHenn.,Suillaceae)(Jägerset al.1987)and isaccompaniedbyaseriesofcolourlessanaloguescontainingfive, fourandthreeacetylresidues.Cyclovariegatinoccursinthismushroomasthecolourlessperacetateoftheleucoform(Edwards&Gill1973).

ThemajorpigmentsoftheorderBoletalesaretheyellowpulvinicacids(39)thatareformedthroughlactoneformation,aftertheterphenyl-

quinoneringhasbeenoxidizedandopened.Theunsubstitutedparentcompound,pulvinicacid,onlyoccursintheformofitsmethylesternamedvulpinicacid.Xerocomicandvariegaticacidsplaythemost importantrolebeingresponsibleforthebluecoloursacquiredinmanyboletesaftertheirfruitingbodiesareinjured,whichresultsintheoxidationoftheseacidstothecorrespondingbluechinonmethidanions(40).PulvinicacidsareespeciallywidespreadinmushroomsbelongingtotheGomphidiaceaeandSuillaceaefamilies,tothegeneraGomphidiusFr.andSuillusGary.Theyellowpigmentgomphidicacid(39)wasfoundforthefirsttimeintheSlimySpike-cap G. glutinosus(Schaeff.exFr.)Fr.(Knight&Pattenden1976).

Theyellow-browncapandstemoftheLarchBoleteSuillus grevillei (Klotzsch)Sing.containatleast11yellow,orangeandredpigmentsderivedfromdecarboxylatedpulvinicacids,ofwhich3',4',4-trihydroxypulvinone(41)isthemajorpigment(Besl&Bresinsky1997).Cyclovariegatin(37)isalsopartlyresponsibleforitscolour(Edwards&Gill1973).

Inthepathwayleadingtoatromentin,insteadoftwoC-CbondsonlyoneC-Cbondmaybeformed.Theresultinglactonisationthenyieldsgrevil-lins(42).GrevillinsA,B,CandDareagroupofcharacteristicorangetored2H-pyran-2,5(6H)dionepigmentsthatoccuronlyinthefruitingbodyof

OO

O

O

O

HO

OH

CH3

O

O

OHOH

HO

O

HO

R

O

O

OHOH

OHHO

OO

36. spiromentin A 37. cycloleucomelone, R = H 38. thelephoric acidcyclovariegatin, R = OH

OO

R

R

OH

HO

O OH

R13

2

OH

OO

O–

HO

O O–

RO O

39. atromentic acid, R1 = R2 = R3 = H 40. chinonmethid anion of xerocomic acid, R = Hxerocomic acid, R1 = H, R2 = OH, R3 = H chinonmethid anion of variegatic acid, R = OHgomphidic acid, R1 = H, R2 = R3 = OHisoxerocomic acid, R1 = OH, R2 = R3 = Hvariegatic acid, R1 = OH, R2 = OH, R3 = H

OO

OHOH

HO

HOO

HO OH

O

OR

R

RR

1

23

4O

O O

O

OHHO

41. 3',4',4-trihydroxypulvinone 42. grevillin A 43. gomphilactonegrevillin Bgrevillin Cgrevillin D

O

O

HOOH

O

O

OH OH

R

O

O

OO

HO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O

OHO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O

44. xerocomorubin, R = H 45. badione A 46. norbadione Avariegatorubin, R = OH

OO

O

O

O

HO

OH

CH3

O

O

OHOH

HO

O

HO

R

O

O

OHOH

OHHO

OO


OO

R

R

OH

HO

O OH

R13

2

OH

OO

O-

HO

O O-

RO O


OO

OHOH

HO

HOO

HO OH

O

OR

R

RR

1

23

4O

O O

O

OHHO

41. 3 ,4 ,4 trihydroxypulvinone 42. grevillin A 43. gomphilactonegrevillin Bgrevillin Cgrevillin D

O

O

HOOH

O

O

OH OH

R

O

O

OO

HO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O

OHO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O


OO

O

O

O

HO

OH

CH3

O

O

OHOH

HO

O

HO

R

O

O

OHOH

OHHO

OO


OO

R

R

OH

HO

O OH

R13

2

OH

OO

O-

HO

O O-

RO O


OO

OHOH

HO

HOO

HO OH

O

OR

R

RR

1

23

4O

O O

O

OHHO


O

O

HOOH

O

O

OH OH

R

O

O

OO

HO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O

OHO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O


OO

O

O

O

HO

OH

CH3

O

O

OHOH

HO

O

HO

R

O

O

OHOH

OHHO

OO


OO

R

R

OH

HO

O OH

R13

2

OH

OO

O-

HO

O O-

RO O


OO

OHOH

HO

HOO

HO OH

O

OR

R

RR

1

23

4O

O O

O

OHHO


O

O

HOOH

O

O

OH OH

R

O

O

OO

HO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O

OHO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O


94


mushroomsbelongingtothegenusSuillus Gray.S. grevillei(Klotzsch)Sing.andS. luteus(L.exFr.)S.F.(SlipperyJack)containgrevillinsA,BandC,S. granulatus(L.exFr.)O.Kuntze(WeepingBolete) containsgrevillinsB,CandD,ofwhichthemajorpigmentisgrevillinD(Beslet al.1974).

Thecolourless,buteasilyoxidisable1,2,4-tri-hydroxybenzeneanditsderivativescommonlyoccurinmushroomsbelongingtotheGomphi-diaceaefamilyandtothegenusSuillus Gray.Theoxidationproductsof1,2,4-trihydroxybenzeneincludetheredgomphilactone(43)andthecor-respondingbiphenyls.Variegatorubin(44)andxerocomorubin(44)exemplifytheredpigmentsformedfrompulvinicacidsbythesecondlactoneringproduction(Besl&Bresinsky1997).

HighconcentrationsofradionuclidesoccurringinthefruitingbodiesoftheBayBoleteBoletus badius(Fr.)Fr.(BoletusFr.,Boletaceae)afterthenuclearreac-toraccidentatChernobylhavebeenascribedtothecomplexationof137Csbythesocallednaphthalenoidpulvinicacidsthatoccurastheirpotassiumsaltsinthecapskinofthistoadstool.ThemaincompoundsarebadioneA(45)andnorbadioneA(46)thatareresponsibleforthechocolatebrownandgoldenyellowcoloursofcapskinofthisboleteandrelatedboletespecies(Aumannet al.1989).

NorbadioneA(46)isthedominatingcompoundinthedyingmushroomPisolithus arrhizus(Scop.)Rauschert(PisolithusAlb.&Schwein,Scleroder-mataceae)whereitoccursinamountofover25%ofthedryweightofthefungus.BadioneA(45)andseveralsimilarcompoundsareminorcomponents(Winneret al.2004).

Oxidativecouplingoftwomoleculesofxerocomicacid(39)yieldsbrightyellowsclerocitrin(47)oc-curringinthefruitingbodiesofthecommonEarthBallScleroderma citrinumPers. (SclerodermaPers.,Sclerodermataceae)togetherwithnorbadioneA(46)asthemainpigments,whichareaccompa-niedbyxerocomicacid(39)andbadioneA(45)(Winneret al.2004).

Sclerocitrinisthemainpigmentofthelemon-yellowcolouredstalkbaseofthePepperyBoleteChalciporus piperatus (Bull.)Bataille(Chalciporus Bataille,Boletaceae).Itisaccompaniedbythesec-ondyellowpigmentchalcitrin(48),norbadioneA(46),variegaticacid(39)andvariegatorubin(44)(Winneret al.2004).

Thedecarboxylationproductsofpulvinicacids,2,5-diarylcyclopentenones,appearinfungialmostasfrequentlyasterphenylquinones.Typicalexamplesarechamonixin(49),involutin(49)andthemorehighlyoxidisedgyrocyanin(50)andgyroporin(50).

OO

OHOH

HO

HOO

HO OH

O

OR

R

RR

1

23

4O

O O

O

OHHO

41. 3 ,4 ,4 trihydroxypulvinone 42. grevillin A, R1 = R3 = R4 = H, R2 = OH 43. gomphilactonegrevillin B, R1 = R3 = H, R2 = R4 = OHgrevillin C, R1 = R2 = R4 = OH, R3 = Hgrevillin D, R1 = R3 = R4 = OH, R2 = HO

O

O

O

O

HO

OH

CH3

O

O

OHOH

HO

O

HO

R

O

O

OHOH

OHHO

OO


OO

R

R

OH

HO

O OH

R13

2

OH

OO

O-

HO

O O-

RO O


OO

OHOH

HO

HOO

HO OH

O

OR

R

RR

1

23

4O

O O

O

OHHO


O

O

HOOH

O

O

OH OH

R

O

O

OO

HO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O

OHO

O

O

O

HO HO

HOOC

OH

OH

HOOC

O


95


Theyoccure.g.inseveralfamiliesofBoletales,inthegeneraChamonixiaRolland(Boletaceae),GyrodonOpat.(Paxillaceae), GyroporusQuél.(Gyroporaceae), LeccinumGray(Boletaceae),MelanogasterCorda(Melanogasteraceae),Paxillus Fr.(Paxillaceae)andseveralotherfamiliesandgenera.Thepigmentsareresponsiblefortheconspicuousdeepbrownandbrightbluecolourreactionsobservedwhenthefruitingbodiesofmushroomsarebruised.InvolutinoccursinP. involutus (BatschexFr.)Fr.(chamonixinisaminorcompound);chamonixinisaconstituentinC. caespitosa RollandandgyrocyanininG. cya- nescens(Bull.exFr.)Quél. Thecolourchangesofthelattermushroomareassociatedwiththerelatedme-taboliteofgyrocyanin,whichisoxidisedtotheblueanion(51)(Felinget al.2001;Hanson2008b).

TheprenylatedcompoundsoccuronlyrarelyinBoletalesbeingbiosynthesisedfrom3,4-dihy-droxybenzoicacid(Besl&Bresinsky1997).Thearomaticringoftenbearsanadditionalfarnesylorgeranylgeranylside-chainderivedfromtheterpenoidpathway.Suillin(52)isanexampleofacetylatedandprenylated1,2,4-trihydroxybenzene

thatoccursinS. granulatus (L.exFr.)O.Kuntze.Itsoxidationproductsareresponsibleforthecaps’browncolour.Prenylatedbenzoquinones,corre-spondingto1,2,4-trihydroxybenzene(mentionedabove),mostlyappearasmeroterpenoidsnamedboviquinones.Boviquinone-3(2,5-dihydroxy-3-farnesyl-1,4-benzoquinone)isbiosynthesisedbyChroogogompus rutilus (Schaeff.)O.K.Mill.,Chroogomphus (Singer) O.K. Mill. (Gomphi-diaceae),bovinoquinone-4(2,5-dihydroxy-3-gera-nylgeranyl-1,4-benzoquinone,53)isanexampleofprenylatedbenzoquinonesfoundinSuillus bovinus (L.)Roussel.(Mühlbaueret al.1998).Theredpigmenttridentoquinone(54)isthemainpigmentofS. tridenticus (Bres.) Singer,whichisrelatedtothelinearboviquinone-4(53)fromS. bovinus (L.)Roussel.Inthemushroom,tridentoquinoneisaccompaniedbyseveralcompoundsofsimilarstructure(Langet al.2008).MushroomsofthegenusRhizopogon Fr.(i.e.Rhizopogon pumilionum (Ade)Bataille),closelyrelatedtothegenusSuil-lus Gray,containrhizopogone(55)asthemainpigment(Langet al.2009).

O

O HO

HH

O

OO

COOH

OH

O

HO

O

O

HO

HOOC

OH

OOH

O

H

H

OH

HO O

HOOC

COOH

O

OH

HO

H

47. sclerocitrin 48. chalcitrin

O

HO OH

HO OH

R

O

HO

HO OH

O

R

HO

OO

OO-

49. chamonixin, R = H 50. gyrocyanin, R = H 51. blue anion of gyrocyanininvolutin, R = OH gyroporin, R = OH

OHOH

OH3C

O

CH3 CH3 CH3 CH3

CH3

52. suillin

CH3CH3

CH3

OH

O

O

HO

CH3

H3C CH3CH3

H

CH3

H3C

H3C

O

OH

O

OCH3CH3

CH3

OH

O

O

HO

H3C

CH3

53. boviquinone 4 54. tridentoquinone 55. rhizopogone

HN CH3H3COOC

O

CH3

O

H

56.melanocrocin

CH3 CH3

CH3 CH3

H3C CH3

H3C CH3CH3

H3C

O

O

57. canthaxanthin

O

O HO

HH

O

OO

COOH

OH

O

HO

O

O

HO

HOOC

OH

OOH

O

H

H

OH

HO O

HOOC

COOH

O

OH

HO

H


O

HO OH

HO OH

R

O

HO

HO OH

O

R

HO

OO

OO-


OHOH

OH3C

O

CH3 CH3 CH3 CH3

CH3

52. suillin

CH3CH3

CH3

OH

O

O

HO

CH3

H3C CH3CH3

H

CH3

H3C

H3C

O

OH

O

OCH3CH3

CH3

OH

O

O

HO

H3C

CH3


HN CH3H3COOC

O

CH3

O

H

56.melanocrocin

CH3 CH3

CH3 CH3

H3C CH3

H3C CH3CH3

H3C

O

O

57. canthaxanthin

O

O HO

HH

O

OO

COOH

OH

O

HO

O

O

HO

HOOC

OH

OOH

O

H

H

OH

HO O

HOOC

COOH

O

OH

HO

H


O

HO OH

HO OH

R

O

HO

HO OH

O

R

HO

OO

OO-


OHOH

OH3C

O

CH3 CH3 CH3 CH3

CH3

52. suillin

CH3CH3

CH3

OH

O

O

HO

CH3

H3C CH3CH3

H

CH3

H3C

H3C

O

OH

O

OCH3CH3

CH3

OH

O

O

HO

H3C

CH3

53. boviquinone-4 54. tridentoquinone 55. rhizopogone

HHCN 3H3COOC

O

CH3

O

H

56. melanocrocin

CH3 CH3

CH3 CH3

H3C CH3

H3C CH3CH3

H3C

O

O

57. canthaxanthin

96


Melanocrocin(56)isauniquebrilliantyellowpolyenepigment,withboundphenylalanine,iso-latedfromthesubterraneanfungusMelanogaster broomeianusthatresembletruffles(Aulingeret al.2001).

3 Cantharellales

Carotenoidsarenotwidespreadinhigherfungiastheyareinplants;nevertheless,theywereisolatedfromseveralyellowpigmentedCantharellusJuss.(Cantharellaceae)species.TheGoldenChanterelleC. cibarius Fr.pigmentmixturewasfoundtoconsistmainlyofβ-caroteneandalsopresentwerelycopene,α-caroteneandtwoothercarotenes,probablytheγ-andδ-isomersorthexanthophylcanthaxanthin(57)thatwasfoundinthepinktored-orangeCin-nabarChanterelleC. cinnabarinus(Schwein.)Sch-wein.asthemainpigment(Haxo1950;Hanson2008b).

4 Hymenochaetales

Styrylpyronehispidin(25)wasoriginallyisolatedasthemainconstituentoftheplantpathogentheChagaFungus Inonotus hispidus (Bull.)P.

Karst.,thepolyporewithared-brownfruitingbody(Bu’Locket al.1962),whereitisaccompa-niedbybisnoryangonin(25),hypholominB(58)andtheyellowpigmenthispolon(26,R= CH3)(Aliet al.1996).Thesepigmentsalsooccurinseveralmushroomsof theHymenochaetaceaefamily,e.g.inInonotus P.Karst.,OnniaP.KarstenandPhellinusQuél.speciesandinthegenusHy-pholoma(Fr.)P.Kumm.oftheStrophariaceaefamily(Agaricales).InoscavinA,reportedtobeafreeradicalscavenger,isolatedfromthefruit-ingbodiesofthemushroomP. xeranticus(Berk.)Pegler(Phellinus,Hymenochaetaceae)hasbeenassignedthefusedstyrylpyronestructure(59),whichrelatesinoscavinAcloselytohispidin(25)andthencetohypholominB(58).

5 Polyporales

SpecieswithintheorderPolyporalesaresapro-trophicandmostofthemwood-rotters.ThePoly-poraceaeareafamilyofsuchwood-decayfungithatcontainpigmentsmostlyderivedfrompolyporicacidsandterphenylquinones.Thedarkredpoly-poricacid(33),theparentcompoundofnumerousterphenylquinonesandrelatedcompounds,isthemajorcomponentofHapalopilus nidulans (Fr.)

O

O HO

HH

O

OO

COOH

OH

O

HO

O

O

HO

HOOC

OH

OOH

O

H

H

OH

HO O

HOOC

COOH

O

OH

HO

H


O

HO OH

HO OH

R

O

HO

HO OH

O

R

HO

OO

OO-


OHOH

OH3C

O

CH3 CH3 CH3 CH3

CH3

52. suillin

CH3CH3

CH3

OH

O

O

HO

CH3

H3C CH3CH3

H

CH3

H3C

H3C

O

OH

O

OCH3CH3

CH3

OH

O

O

HO

H3C

CH3


HN CH3H3COOC

O

CH3

O

H

56.melanocrocin

CH3 CH3

CH3 CH3

H3C CH3

H3C CH3CH3

H3C

O

O

57. canthaxanthin

O

O HO

HH

O

OO

COOH

OH

O

HO

O

O

HO

HOOC

OH

OOH

O

H

H

OH

HO O

HOOC

COOH

O

OH

HO

H


O

HO OH

HO OH

R

O

HO

HO OH

O

R

HO

OO

OO-


OHOH

OH3C

O

CH3 CH3 CH3 CH3

CH3

52. suillin

CH3CH3

CH3

OH

O

O

HO

CH3

H3C CH3CH3

H

CH3

H3C

H3C

O

OH

O

OCH3CH3

CH3

OH

O

O

HO

H3C

CH3


HHCN 3H3COOC

O

CH3

O

H

56. melanocrocin

CH3 CH3

CH3 CH3

H3C CH3

H3C CH3CH3

H3C

O

O

57. canthaxanthin

O

O HO

HH

O

OO

COOH

OH

O

HO

O

O

HO

HOOC

OH

OOH

O

H

H

OH

HO O

HOOC

COOH

O

OH

HO

H


O

HO OH

HO OH

R

O

HO

HO OH

O

R

HO

OO

OO-


OHOH

OH3C

O

CH3 CH3 CH3 CH3

CH3

52. suillin

CH3CH3

CH3

OH

O

O

HO

CH3

H3C CH3CH3

H

CH3

H3C

H3C

O

OH

O

OCH3CH3

CH3

OH

O

O

HO

H3C

CH3


HHCN 3H3COOC

O

CH3

O

H

56. melanocrocin

CH3 CH3

CH3 CH3

H3C CH3

H3C CH3CH3

H3C

O

O

57. canthaxanthin

97


P.Karst.(Hapalopilus P.Karst.)amountingupto43%ofitsdryweight. BetulinansA(60)andB(61)aretwosimpleterphenylquinonesrecentlyfoundintheplantpathogenLenzites betulina (L.)Fr.(LenzitesFr.)(Leeet al.1996;Gill1999).Thelabile2,3,4-trihydroxycinnamylalcoholisthebuild-ingblockofthepurpurogallin(benzotropolone)derivativefomentariol(62)producedbytheplantpathogen,theTinderFungus,Fomes fomentarius(L.)Fr.ofthegenusFomes(Fr.)Fr.(Polyporaceae)(Steglich&Zechlin1978).

PigmentswithaphenoxazinechromophorewidelyoccurinlichensandtoasmallerextentinhigherfungiofthePolyporaceaefamily.Thecinnabarredpigmentofthewood-rottingfungusPycnoporus cinnabarinus(Jacq.)P.Karst.(Pycnopo-rusP.Karst.)is2-amino-3H-phenoxazin-3-one-1,9-dicarboxylicacidnamedcinnabaricacid(63).Itisbiosynthesizedfrom3-hydroxyanthranilicacidunitsformedasthetryptophantransformationproducts(Gripenberg1958a).

ThecobaltCrustFungusTerana caerulea (Lam.)Kuntze(TeranaAdans.)ofthePhanerochaetaceaefamilycontainscorticinsA(64),BandCasthecolourlessquinhydronesthatareoxidizedtotheindigo-bluepigmentinhymenalsurface (Briggset al.1976).ThesaprophyticfungusPhanerochaete sanguine (Fr.)Pouzar (Phanerochaete P.Karst.)con-tainsxylerythrin-typepigments(65).Theirstruc-turessuggestabiosynthesisfromthreemoleculesofarylpyruvicacids.Thewoodinfectedbythisfungusisthencoloureddarkredbyitsmycelium(Gripenberg1965;Gripenberg&Martikkala1970).

Thestrikingyellowishororange-colouredfruit-ingbodiesofthewood-rottingediblemushroomLaetiporus sulphurous(Bull.)Murrill(LaetiporusMurrill),belongingtotheFomitopsidaceaefamily,containsnon-isoprenoidpolyeneknownaslaetiporicacidA(predominantlyoccurringasthe7-cis-isomer,66)and2-dehydro-3-deoxylaetiporicacidA(67)asthemainpigments(Davoliet al.2005).

6 Russulales

Apartfromcarotenoids,onlyafewlowerter-penoidsarecolouredcompounds.ThecolouroftheinjuredfleshaswellasofthelatexofseveralLactariusPers.(Russulaceae)speciesowntotheircolourchangestosesquiterpenoids.TheyoungfruitingbodyofL. deliciosus (L.exFr.)S.F.Grayisfirstcarrot-coloured,butslowlyturnsgreenonaging.TheyoungL. deterrimusGrögerfruit-ingbody ispalepeachcolouredandbecomesapricotcolouredwithagreyishgreenshadesonaging.Oncutting,L. deterrimusyieldssaffronororangecolouredlatex.Thesecolourchangesareduetosesquiterpenoidsderivedfromazulene.ThecompoundsresponsibleforthesecolourchangesinL. deliciosusaretheblue lactarazulene, i.e.1,4-dimethyl-7-(1-methylethenyl)azulene(68),andlipophilicred-violetlactaroviolin,i.e.4-methyl-7-(1-methylethenyl)azulene-1-carbaldehyde(68).However,neitherlactarazulenenorlactaroviolinoccursassuch.Theorangecolourofthefungusisduetothelabileandeasilyoxidizabledihy-

O

O

O

OHOH

O

HO

HO

HO

O

CH3

HO

HO

O O

O

O

OHOH

58. hypholomin B 59. inoscavin A

O

OOCH3

H3COO

OOCH3

O

HOOH

HO

HO

OHOH

O

O

N

OHCOOH

O

NH2

60. betulinan A 61. betulinan B 62. fomentariol 63. cinnabarinic acid

H3CO

HO

O

O

OCH3

OHOH

OCH3

O

O

O

HO

HO

R

64. corticin A 65. xylerythrin, R = H peniophorin, R = OH

HOOCOH

CH3

H3C O

66. laetiporic acid A

HOOC

OH3C

CH3

67. 2-dehydro-3-deoxylaetiporic acid A

CH2

H3C

H3C

R CH2H3C

RO

H3C H3C

CH3

H3CO

68. lactarazulene, R = CH3 69. dihydroazulen-1-ol (R = H) 70. 1,3,5,7(11),9-pentaenyl-14-guaianallactaroviolin, R = CH=O

O

O

O

OHOH

O

HO

HO

HO

O

CH3

HO

HO

O O

O

O

OHOH


O

OOCH3

H3COO

OOCH3

O

HOOH

HO

HO

OHOH

O

O

N

OHCOOH

O

NH2


H3CO

HO

O

O

OCH3

OHOH

OCH3

O

O

O

HO

HO

R

64. corticin A 65. xylerythrin, R = Hpeniophorin, R = OH

HOOCOH

CH3

H3C O


HOOC

OH3C

CH3

67. 2 dehydro 3 deoxylaetiporic acid A

CH2

H3C

H3C

R CH2H3C

RO

H3C H3C

CH3

H3CO

68. lactarazulene, R = CH3 69. dihydroazulen 1 ol (R = H) 70. 1,3,5,7(11),9 pentaenyl 14 guaianallactaroviolin, R = CH=O

98


droazulen-1-ol(69,R=H)ortotheirstearates,69,R=CO[CH2]16CH3.Recently,threeotherredazulenepigmentshavebeenisolatedfromthefruitingbodiesofL. deliciosusbeing7-acetyl-4-methylazulene-1-carbaldehyde,7-(1,2-dihydroxy-1-methylethyl)-4-methylazulene-1-carbaldehydeand7-acetyl-4-methylazulene-1-carboxylicacid(Xanget al.2006;Zhou&Liu2010).Theredpigment1,3,5,7(11),9-pentaenyl-14-guaianal(70)wasfoundinL. sanguifluus(Paulet)Fr.,theli-pophilicpigment1-hydroxymethyl-4-methyl-7-(1-methylethenyl)azulene stearate; 68, R =CH2OCO[CH2]16CH3,isresponsibleforthebril-liantbluecolouroftheIndigoMilkCapL. indigo (Schwein.)Fr.(nativetoAmericaandAsiaandalsoreportedfromsouthernFrance)(Harmonet al.1980;Ayer&Browne1981;Koulet al.1985;DeRosa&DeStefano1987).

ThemilkyjuiceofL. scrobiculatus(Scop.)Fr.turnsrapidlyfromwhitetoyellow.Arangeoflactaraneandsecolactaranesesquiterpenoids,analoguesoftheaboveazulenes,havebeeniso-lated(Bosettiet al.1989).Thestructuresof

uvidinAandB(71)illustratethebroadvarietyofcompoundsfoundinL. uvidus (Fr.)Fr.Drimanesesquiterpenoidslikedrimenol(72)anduvidinshavesofarbeenfoundonlyinL. uvidus,whichhasawhitelatexrapidlyturningvioletonexpo-suretotheair.

IntactfruitingbodiesofLactarius fuliginosus (Krapf )Fr.andL. picinus Fr. containtheisoprenoidquinolstearateof4-methoxy-2-(3-methylbut-2-enyl)phenol(73).Thepink-redstainandacridtastethatdevelopswhenthetoadstoolisbruisedareduetoitshydrolysisfollowedbyoxidationtoavarietyofredbenzofuransandchromenes(DeBernardiet al.1992).

Thepalegreenaminobenzoquinoneblennione(74)occursinthefruitbodiesofthecommontoadstool, the Slimy Milkcap Lactarius blennius (Fr.)Fr.Itisprobablybiosynthesizedusing3,6-dihydroxyanthranilicacidunits(Spiteller&Steglich2002).Biosyntheticallycloselyrelatedtobennioneistheredpigmentlilacinone(75),whichisresponsibleforthevioletcolourofLactarius lilacinus(Lasch)Fr.(Spitelleret al.2003).

O

O

O

OHOH

O

HO

HO

HO

O

CH3

HO

HO

O O

O

O

OHOH


O

OOCH3

H3COO

OOCH3

O

HOOH

HO

HO

OHOH

O

O

N

OHCOOH

O

NH2


H3CO

HO

O

O

OCH3

OHOH

OCH3

O

O

O

HO

HO

R


HOOCOH

CH3

H3C O


HOOC

OH3C

CH3


CH2

H3C

H3C

R CH2H3C

RO

H3C H3C

CH3

H3CO


O

O

O

OHOH

O

HO

HO

HO

O

CH3

HO

HO

O O

O

O

OHOH


O

OOCH3

H3COO

OOCH3

O

HOOH

HO

HO

OHOH

O

O

N

OHCOOH

O

NH2


H3CO

HO

O

O

OCH3

OHOH

OCH3

O

O

O

HO

HO

R


HOOCOH

CH3

H3C O


HOOC

OH3C

CH3


CH2

H3C

H3C

R CH2H3C

RO

H3C H3C

CH3

H3CO


O

O

O

OHOH

O

HO

HO

HO

O

CH3

HO

HO

O O

O

O

OHOH


O

OOCH3

H3COO

OOCH3

O

HOOH

HO

HO

OHOH

O

O

N

OHCOOH

O

NH2


H3CO

HO

O

O

OCH3

OHOH

OCH3

O

O

O

HO

HO

R


HOOCOH

CH3

H3C O


HOOC

OH3C

CH3


CH2

H3C

H3C

R CH2H3C

RO

H3C H3C

CH3

H3CO


O

O

O

OHOH

O

HO

HO

HO

O

CH3

HO

HO

O O

O

O

OHOH


O

OOCH3

H3COO

OOCH3

O

HOOH

HO

HO

OHOH

O

O

N

OHCOOH

O

NH2


H3CO

HO

O

O

OCH3

OHOH

OCH3

O

O

O

HO

HO

R


HOOCOH

CH3

H3C O


HOOC

OH3C

CH3


CH2

H3C

H3C

R CH2H3C

RO

H3C H3C

CH3

H3CO


99


Analkaloidalpigmentnecatarone(76),itsde-hydrodimer(77,R1=R2=OH)prevailinginagedfruitingbodiesandthe10-deoxydehydrodimer(77,R1=H,R2=OH)aretheprincipalpigmentsofthegreen-brownfleshandcapskinofLacta- rius turpis(Weinm.)Fr.(Fugmannet al.1984,Klamannet al.1989).

Ochroleucinsarethemainpigmentsofthefruit-ingbodiesoftheCommonYellowRussula,Russula ochroleucaPers.andR. viscidaKudrna(Russula Pers.,Russulaceae).ThelabileyellowochroleucinA(78) israpidlytransformedtothestableredochroleucinB(79)(Sontaget al.2006).

DimericmeroterpenoidpigmentshavebeenreportedfromtheAlbatrellusGrayspecies(Al-

batrellaceae),whichincludede.g.thepurplepig-mentgrifolinoneB(80),theredketonealbatrellin(81)andavarietyofrelatedcompoundsofthemushroomA. confluens(Alb.&Schwein.)Kotl.&Pouzar(Yanget al.2008).

TheOrangeToothHydnellum aurantiacum(Batsch)P.Karst.(Hydnellum P.Karst.,Peniophora-ceae)colourisderivedfromtheterphenylquinoneatromentin.The3,6-dibenzoylatromentin,namedaurantiacin,wasfirstisolatedasadarkredpig-mentfromthismushroomandsubsequentlyfromvariousHydnellumspecies(Gripenberg1956;Gripenberg1958b).Aurantiacinisaccompaniedwiththecorrespondingleucoformdihydroauran-tiacinandthelephoricacid.

RCH3H3C O

OCH3

OH

H3C

HCH3H3C

CH3

OH

H3C

H

OCH3

OH

CH3

CH3

71. uvidin A, R = H 72. drimenol 73. 4 methoxy 2 (3 methylbut 2 enyl)phenoluvidin B, R = OH

COOH

NH2

OHHOOC

H2NOCH3 O

O

H

H2N

HOOC

O

ON

OH

OO O

OCH3

COOH

NH2 N

N

OH

HO

O

74. blennione 75. lilacinone 76. necatarone

2

N

NR

O OH HO

N

NR

O

1

77. necatarone dehydrodimer

H2C

CH3

OCH3

OCH3

O

H

OH

O

CH3

CH2

O

H2C

CH3

OH

OO

O

CH2

CH3

78. ochroleucin A 79. ochroleucin B

CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

O

80. grifolinone B 81. albatrellin

+

HO

HO

CH3

CH3H3C

H3C O

OHO-

OHN

NO

O

OH

O O

HO

OHHO

O

ON

NOH

O- OH

OH3CH3C CH3

CH3

O O

O

H3C

O

CH3 +

82. sarcoviolin 83. sarcodonin

RCH3H3C O

OCH3

OH

H3C

HCH3H3C

CH3

OH

H3C

H

OCH3

OH

CH3

CH3


COOH

NH2

OHHOOC

H2NOCH3 O

O

H

H2N

HOOC

O

ON

OH

OO O

OCH3

COOH

NH2 N

N

OH

HO

O


2

N

NR

O OH HO

N

NR

O

1


H2C

CH3

OCH3

OCH3

O

H

OH

O

CH3

CH2

O

H2C

CH3

OH

OO

O

CH2

CH3


CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

O


+

HO

HO

CH3

CH3H3C

H3C O

OHO-

OHN

NO

O

OH

O O

HO

OHHO

O

ON

NOH

O- OH

OH3CH3C CH3

CH3

O O

O

H3C

O

CH3 +


RCH3H3C O

OCH3

OH

H3C

HCH3H3C

CH3

OH

H3C

H

OCH3

OH

CH3

CH3


COOH

NH2

OHHOOC

H2NOCH3 O

O

H

H2N

HOOC

O

ON

OH

OO O

OCH3

COOH

NH2 N

N

OH

HO

O


2

N

NR

O OH HO

N

NR

O

1


H2C

CH3

OCH3

OCH3

O

H

OH

O

CH3

CH2

O

H2C

CH3

OH

OO

O

CH2

CH3


CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

O


+

HO

HO

CH3

CH3H3C

H3C O

OHO-

OHN

NO

O

OH

O O

HO

OHHO

O

ON

NOH

O- OH

OH3CH3C CH3

CH3

O O

O

H3C

O

CH3 +


RCH3H3C O

OCH3

OH

H3C

HCH3H3C

CH3

OH

H3C

H

OCH3

OH

CH3

CH3


COOH

NH2

OHHOOC

H2NOCH3 O

O

H

H2N

HOOC

O

ON

OH

OO O

OCH3

COOH

NH2 N

N

OH

HO

O


2

N

NR

O OH HO

N

NR

O

1


H2C

CH3

OCH3

OCH3

O

H

OH

O

CH3

CH2

O

H2C

CH3

OH

OO

O

CH2

CH3


CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

O


+

HO

HO

CH3

CH3H3C

H3C O

OHO-

OHN

NO

O

OH

O O

HO

OHHO

O

ON

NOH

O- OH

OH3CH3C CH3

CH3

O O

O

H3C

O

CH3 +


RCH3H3C O

OCH3

OH

H3C

HCH3H3C

CH3

OH

H3C

H

OCH3

OH

CH3

CH3


COOH

NH2

OHHOOC

H2NOCH3 O

O

H

H2N

HOOC

O

ON

OH

OO O

OCH3

COOH

NH2 N

N

OH

HO

O


2

N

NR

O OH HO

N

NR

O

1


H2C

CH3

OCH3

OCH3

O

H

OH

O

CH3

CH2

O

H2C

CH3

OH

OO

O

CH2

CH3


CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

CH3

O

CH3CH3CH3

CH3

OHH3C

O

O

OH

HO CH3

H3CCH3

O


+

HO

HO

CH3

CH3H3C

H3C O

OHO-

OHN

NO

O

OH

O O

HO

OHHO

O

ON

NOH

O- OH

OH3CH3C CH3

CH3

O O

O

H3C

O

CH3 +


100


7 Thelephorales

ThefruitingbodiesofSarcodon leucopus(Pers.)MaasGeest.&Nannf.(Sarcodon Quél.exP.Karst.,Bankeraceae)containarangeofcompoundsrelatedtoterphenylquinones.Themainpigmentsaretheunusualnitrogenousvioletterphenylquinolssar-coviolins,exemplifiedbysarcoviolonα(82),whichareaccompaniedbytheircolourlessprecursorssarcodonins(83)andstructurallyrelatedcom-pounds(Geraciet al.2000;Caliet al.2004).

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RCH3H3C O

OCH3

OH

H3C

HCH3H3C

CH3

OH

H3C

H

OCH3

OH

CH3

CH3


COOH

NH2

OHHOOC

H2NOCH3 O

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H

H2N

HOOC

O

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OO O

OCH3

COOH

NH2 N

N

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2

N

NR

O OH HO

N

NR

O

1


H2C

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OCH3

OCH3

O

H

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H2C

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OO

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CH2

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CH3

O

CH3CH3CH3

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OHH3C

O

O

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HO CH3

H3CCH3

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O

CH3CH3CH3

CH3

OHH3C

O

O

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HO CH3

H3CCH3

O


+

HO

HO

CH3

CH3H3C

H3C O

OHO-

OHN

NO

O

OH

O O

HO

OHHO

O

ON

NOH

O- OH

OH3CH3C CH3

CH3

O O

O

H3C

O

CH3 +


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RecievedforpublicationDecember29,2010AcceptedaftercorrectionsJanuary15,2011

Corresponding author:

Prof.Ing.JanVelíšek,DrSc.,Vysokáškolachemicko-technologickávPraze,Fakultapotravinářskéabiochemickétechnologie,Ústavchemieaanalýzypotravin,Technická5,16628Praha6,Českárepublikatel.:+420220443175,e-mail:[email protected]

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