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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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Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102
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
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
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
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
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
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
1. agaritine 2. agaricone
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+
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
1. agaritine 2. agaricone
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+
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
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Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.
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
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
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
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
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
1. agaritine 2. agaricone
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
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
91
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102
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
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
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
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
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
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
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
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
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
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
92
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.
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
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
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
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
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
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
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
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
93
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102
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
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
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
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
94
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.
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
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
95
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102
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
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
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
HHCN 3H3COOC
O
CH3
O
H
56. melanocrocin
CH3 CH3
CH3 CH3
H3C CH3
H3C CH3CH3
H3C
O
O
57. canthaxanthin
96
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.
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
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
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
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
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
HHCN 3H3COOC
O
CH3
O
H
56. melanocrocin
CH3 CH3
CH3 CH3
H3C CH3
H3C CH3CH3
H3C
O
O
57. canthaxanthin
97
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102
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
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 = Hpeniophorin, 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
98
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.
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 blen- nius (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
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 = Hpeniophorin, 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
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 = Hpeniophorin, 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
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 = Hpeniophorin, 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
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 = Hpeniophorin, 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
99
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102
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
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
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
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
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
100
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.
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
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
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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
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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]