Pigments of Higher Fungi: A Review

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

Pigments of Higher Fungi: A Review 

Jan VELÍŠEK and Karel CEJPEK 

Department of Food Chemistry and Analysis, Faculty of Food and Biochemical Technology, 

Abstract 

Institute of Chemical Technology in Prague, Prague, Czech Republic 

Velíšek J., Cejpek K. (2011): Pigments of higher fungi – a review. Czech J. Food Sci., 29: 87–102. 

This review surveys the literature dealing with the structure of pigments produced by fungi of the phylum Basidiomycota 

and also covers their significant colourless precursors that are arranged according to their biochemical origin to the 

shikimate, polyketide and terpenoid derived compounds. The main groups of pigments and their leucoforms include 

simple benzoquinones, terphenylquinones, pulvinic acids, and derived products, anthraquinones, terpenoid quinones, 

benzotropolones, compounds of fatty acid origin and nitrogen-containing pigments (betalains and other alkaloids). 

Out of three orders proposed, the concern is only focused on the orders Agaricales and Boletales and the taxonomic 

groups (incertae sedis) Cantharellales, Hymenochaetales, Polyporales, Russulales, and Telephorales that cover most of 

the so called higher fungi often referred to as mushrooms. Included are only the European species that have generated 

scientific interest due to their attractive colours, taxonomic importance and distinct biological activity. 

Keywords: higher fungi; Basidiomycota; mushroom pigments; mushroom colour; pigment precursors 

Mushrooms inspired the cuisines of many cultures 

(notably Chinese, Japanese and European) 

for centuries and many species were used in folk 

medicine for thousands of years. However, little 

is known that mushrooms were a commonly 

used textile dye before the invention of synthetic 

dyes because of the vast range of vivid and rich 

colours achievable (Mussak & Bechtold 2009). 

The chromophores of mushroom dyes contain a 

variety of fascinating organic compounds. Their 

pigmentation may vary with the age and some 

undergo distinctive colour changes on bruising; 

therefore, the colours of mushrooms are one of 

the essential features used in their identification. 

Furthermore, the pigments of mushrooms may 

protect the organism from UV damage and bacterial 

attack or play a role as insect attractants. 

Mushrooms do not contain the pigments that 

dominate in higher plant colours. Chlorophylls and 

anthocyanins are not present in fungi at all; betalains, 

carotenoids and other terpenoids are widespread 

only in some species of higher fungi. Many of the 

pigments of higher fungi are quinones or similar 

conjugated structures that are mostly classified according 

to the perceived biosynthetic pathways, reflecting 

their structure, to pigments derived from (i) 

the shikimate (chorismate) pathway, (ii) the acetatemalonate 

(polyketide) pathway, (iii) the mevalonate 

(terpenoid) pathway, and (iv) pigments containing 

nitrogen. Several review articles covering the literature 

published from its inception during the latter 

half of the 19 th century to the end of 2009 have been 

already published (Gill & Steglich 1987; Gill 

1994, 1996, 1999, 2003; Hanson 2008a,b; Räisänen 

2009; Zhou & Liu 2010). 

The shikimate pathway provides a route to the 

essential amino acids phenylalanine, tyrosine and 

tryptophan via the central intermediates shikimic 

and chorismic acids. Phenylalanine and tyrosine are 

precursors for a wide range of compounds includ- 

Partly supported by the Ministry of Education, Youth and Sports of the Czech Republic, Project No. MSM 6046137305. 

87

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

ing arylpyruvic, cinnamic and benzoic acids that 

represent the building blocks for many pigments of 

higher fungi. Condensation of two arylpyruvic acid 

yields red to brown terphenylquinones and related 

orange to red grevillins. Diarylcyclopentenones, 

responsible for the colour changes in some bruised 

mushrooms, are formed by ring contractions of 

terphenylquinones while oxidative cleavage of the 

hydroxyquinone ring in terphenylquinones and 

rearrangement of thus formed intermediates results 

in a series of yellow and orange lactones known as 

pulvinic (pulvic) acids. Their decarboxylation yields 

the yellow pulvinones that can be oxidised and further 

transformed to a number of structurally related 

products. Reduction of cinnamic acids affords the 

corresponding alcohols that are the building blocks 

of benzotropolone pigments. Tyrosine, hydroxylated 

to 3,4-dihydroxyphenylalanine (DOPA), is 

the precursor of the red-violet betacyanins and the 

orange-yellow betaxanthins. Both amino acids and 

their transformation products can be converted via 

quinones into the heterogeneous dark pigments 

melanins by the enzymatic browning reactions 

(oxidations and polymerisations). Tryptophan is 

transformed to hydroxyanthranilic acids that become 

the precursor of phenoxazines and other nitrogen-containing 

pigments. Benzoquinones can be 

synthesised from very different starting substances 

and via different biochemical pathways, e.g. using 

benzoic acids produced in the shikimate pathway. 

Terpenoid quinones are formed by combination of 

the shikimate pathway with the mevalonate pathway. 

The polyketide pathway yields either aromatic 

ketides or fatty acids. For the aromatic ketides, the 

growing chain stabilises by cyclization reactions 

and partial reduction, whereas for fatty acids, the 

carbonyl groups of the chain are reduced before 

attachment of the next C 2 group. Products of this 

pathway include tetra-, hepta-, octa- and higher 

ketides and compounds of fatty acid origin. Fungi 

contain a range of pigments of octaketide origin 

(e.g. anthraquinones) that are based on the anthra- 

9,10-quinone skeleton with both rings substituted. 

In many cases, anthraquinones are found in fungi 

as the corresponding colourless reduced forms 

88 

(anthranol, anthrone, anthrahydroquinone, and 

oxanthrone derivatives) that may occur in the form 

of various glycosides. Many natural anthraquinones 

are oligomers formed by coupling of two or more 

anthraquinone molecules. These oligomers further 

differ in the points through which monomers are 

attached and may have more than one polymorphic 

form (Velíšek et al. 2007, 2008; Velíšek & 

Cejpek 2008). Styrylpyrones are biosynthesised 

by a combined shikimate and polyketide pathway, 

which otherwise yields various terpenoids including 

carotenoids. 

Various pigments and other fungi constituents 

show important biological activities (antioxidative, 

free radical scavenging, anticarcinogenic, immunomodulatory, 

antiviral, and antibacterial) that 

have generated intensive research interest (Steglich 

1981; Calìa et al. 2003; Liu 2006; Medicinal 

Mushrooms 2008; Schüffler & Anke 2009). 

The taxonomy of the kingdom Fungi (the subkingdom 

Dikarya) is in a state of constant flux; therefore, 

the most recent 2007 classification adopted by a 

coalition of mycologists was used (Thorna et al. 

2007; MycoBank 2010). Out of seven phyla (divisions) 

proposed, the concern of this review only deals with 

the phylum Basidiomycota (“club fungi”) 1 (subphylum 

Agaricomycotina, class Agaromycetes, subclass 

Agaromycetidae)thatcoversmostofthesocalled“higher 

fungi” often referred to as “mushrooms”growing 

in Europe. The referred pigments, not reviewed up 

to now, are arranged according to the mushroom 

orders. Many other pigments were identified in 

fungi indigenous to Australasia. 

1 Agaricales 

The genera Agaricus L., Leucoagarius Locq. ex 

Singer and Macrolepiota Singer of the Agaricaceae, 

including the common mushroom A. bisporus (J.E. 

Lange) Imbach (now cultivated in at least 70 countries 

around the world), contain the glutamic acid 

derived hydrazine agaritine (1) that may be enzymatically 

oxidised at the C-4 hydroxymethyl group 

to the corresponding formyl and carboxyl deriva- 

1 The 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 studied 

only sporadically; the black pigments of the black truffle T. melanosporum are polymeric allomelanins of polyketide 

origin (De Angelis et al. 1996).

O 

H 

N 

N 

H 

HO 

COOH 

O 

H 

N 

N 

H 

NHHO N 

2 H 

O 

H 

N 

N 

H 

COOH 

N 

N N 

H 

NH2 Czech HO J. Food Sci. NH2 

O Vol. 29, 2011, No. 2: 87–102 

O 

H 

N 

N 

H 

HO 

O 

H 

COOH N 

N 

H 

NH2 

COOH 

NH2 

N 

H 

N 

N 

N 

N N 

H 

O 

 

O 

 

1.agaritine 1.agaritine 2.agaricone 

2.agaricone 

HO 

O 

O 

COOH 

COOH 

N 

N 

H 

H 

NH2 NH2 

 

glutamyl4hydroxybenzene 3.γglutamyl4hydroxybenzene 

O 

O 

OH 

OH 

NH 

NH 

 

 

4.2hydroxy4imino 

4.2hydroxy4iminocyclohexa2,5dienone 

cyclohexa2,5dienone 

HOOC 

O 

COO 

N 

- 

+ 

COO 

+ O 

N 

- 

N 

COO O 

+ 

N 

O 

- 

COOH 

+ 

N COO - 

1.agaritine 2.agaricone 

HO 

O 

N 

H 

COOH 

NH2 

3.γglutamyl4hydroxybenzene 4.2hydroxy4imino 

HOOC 

COO 

O 

N 

O 

HOOC N COOH 

- 

+ 

+ 

COO 

O 

N 

OH 

H 

H 

 

- 

N 

+ 

N 

COO O 

O 

HOOC N COOH 

 

HOOC N COOH 

H 

- 

1.agaritine 2.agaricone 

1. agaritine 2. agaricone 

HO 

O 

N 

H 

HO 

COOH 

NH2 O 

N 

H 

COOH 

NH2 

O 

OH 

NH 

O 

NH 

OH 

 

3.γglutamyl4hydroxybenzene 4.2hydroxy4imino 

3. γ-glutamyl-4-hydroxybenzene 4. 2-hydroxy-4-iminocyclohexa-2,5-dienone cyclohexa2,5dienone 

 

HOOC 

COO 

O 

N 

O 

HOOC N COOH 

5.muscapurpurin 6.muskaaurinI 7.muskaaurinI 

– 

+ 

COO 

+ O 

N 

OH 

H 

H 

– 

COO O 

+ 

N 

N 

O 

COOH 

HOOC N COOH 

HOOC N COOH 

H 

– 

+ 

N 

COOH 

COO 

HOOC N COOH 

H 

– 

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

COOH 

O 

COOH 

tives, which are hydrolysed to 4-(hydroxymethyl)- OH and yellow muscaflavin (12). Muscaurin I (6) and 

phenylhydrazine and 4-carboxymethylbenzoic acid, muscaurin II (7) are derived from unusual nonpro- 

respectively. 4-(Hydroxymethyl)phenylhydrazine is tein amino acids ibotenic acid and stizolobic acid, 

HOOC N COOH HOOC N COOH 

HOOC N COOH 

HOOC N COOH 

oxidised to theH corresponding diazonium H 

H 

cation. respectively, and are the major H agaric pigments. 

 

 

 

 

The metabolic fate of agaritine has been linked Pigments named muscaurins III–VII are mix- 

5.muscapurpurin with the carcinogenity of the6.muskaaurinI mushroom (Walton 7.muskaaurinII tures of pigments derived 8.vulgaxanthinI from common proteno- 

et al. 2001). The yellow pigment characteristic of genous amino acids. Muscaurin III is a mixture of 

CONH2 the yellow-staining A. xanthodermus Genev. and of vulgaxanthin I (8), known as (S)-glutamine-beta- 

some other Agaricus species is caused by another xanthin, miraxanthin III (9), known as (S)-aspartic 

+ 

azaquinone N COO metabolite agaricone (2) that forms by acid-betaxanthin, and a betaxanthin derived from 

oxidation of the corresponding leucophenol in the 2-aminoadipic acid. Muscaurin IV is a mixture of 

damaged tissue. The agaritine analogues derived vulgaxanthin I and miraxanthin III. Muscaurin 

from 4-aminophenol γ-glutamyl-4-hydroxybenzene V is a mixture of vulgaxanthin II (10), known as 

(3) readily oxidise to the corresponding quinone (S)-glutamic acid-betaxanthin, indicaxanthin (11), 

HOOC N COOH 

via γ-glutamyl-3,4-dihydroxybenzene. H 

This quinone known as (S)-proline-betaxanthin, and betaxan- 

decomposes to 2-hydroxy-4-iminocyclohexa-2,5thins derived from valine and leucine. Muscaurin VI 

dienone (4), which imparts a pink-red colour to some is a mixture of vulgaxanthin II and indicaxanthin. 

agarics (e.g. to A. bisporus) (Hanson 2008a,b). Muscaurin VII is derived from histidine (Muso 

The striking orange-red pigments of the cap of 1976; Li & Oberlies 2005). 

fly agaric Amanita muscaria (L.) Hook. (Amanita Fly agaric and mushrooms of the genus Hygrocybe 

Pers., Amanitaceae) are a mixture of the purple (Fr.) P. Kumm. (Hygrophoraceae), e.g. H. conica 

betacyanin muscapurpurin (5), orange betaxan- (Schaeff.) P. Kumm., commonly known as the witch’s 

thins muscaurins (muscaaurins) I–VII (6 and 7) hat, synthesise the yellow pigment muscaflavin (12), 

- 

+ 

N COO 

HOOC N COOH 

H 

 

- 

COOH 

+ 

N COO 

HOOC N COOH 

H 

 

- 

O 

HOOC N COOH 

H 

 

 

9.miraxanthinIII 10.vulgaxanthinII 11.indicaxanthin 12.muscaflavin 

2- 

CH3 

COOH 

O 

R + 

N CH3 

N 

O O 

O V O O 2 H 

O O 

H3C N 

HOOC N 

O 

COOH 

H 

CH3 

 

 

+ 

CONH2 + 

N COO 

HOOC N COOH 

H 

 

13.hygroaurins(R=aminoacidresidue) 14.amavadin 

CH3 OCH3 H3CO OH 

O 

HO 

OH 

O OH 

O OH OH 

H3CO OH OH O 

OH 

CH3 

OH OH O 

OH 

RO 

CH3 

- 

+ 

N COO 

HOOC N COOH 

H 

 

- 

COOH 

+ 

N COO 

HOOC N COOH 

H 

 

- 

O 

H 

N COOH 

N 

N 

N N 

H 

H 

HO 

NH2 O 


O 

HO 

O 

OH 

COOH 

N 

H 

NH2 9.miraxanthinIII 10.vulgaxanthinII NH 

11.indicaxanthin 

 

H 

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

COOH 

R + 

N 

HOOC 

COO 

O 

N 

H3 

HOOC N COOH 

O 

H 

 

 

13.hygroaurins(R=aminoacidresidue) 

HOOC N COOH 

CH3 OCH3 O 

HO 

OH OH O 

H3CO OH 

O OH OH 

H3CO C 

OH O OH 

15.fallacinol 16.(3R,3R,M)flavomannin6,6diOmeth 

– 

COO 

+ 

+ O 

N 

OH 

H 

H 

– 

COO O 

+ 

N 

N 

O 

COOH 

HOOC N COOH 

HOOC N COOH 

H 

– 

COOH 

+ 

N COO 

HOOC N COOH 

H 

– 


CONH2 + 

N COO 

HOOC N COOH 

H 

– 

+ 

N COO 

HOOC N COOH 

H 

– 

COOH 

+ 

N COO 

HOOC N COOH 

H 

– 

CONH2 + 

N COO 

HOOC N COOH 

H 

O 

9. miraxanthin III 10. vulgaxanthin II 11. indicaxanthin 

HOOC N COOH 

H 

12. muscaflavin 

– 

+ 

N COO 

HOOC N COOH 

H 

– 

COOH 

+ 

N COO 

HOOC N COOH 

H 

– 

O 

HOOC N COOH 

H 

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

CH3 

COOH 

O N CH3 

R + 

N 

O O 

O V O O 2 H 

O O 

H3C N 

HOOC N 

O 

COOH 

H 

CH3 

+ 

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

CH3 OCH3 O 

HO 

OH OH O 

OH OH O 

H3CO OH 

O OH OH 

OH 

OH 

H3CO CH RO 

3 

OH O OH 

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

(3R)-torosachrysone, R = CH3 

15.fallacinol 16.(3R,3R,M)flavomannin6,6diOmethylether17.(3R)atrochrysone,R=H 

(3R)torosachrysone,R=CH3 

CH3 

89 

R 

COOH 

+ 

N 

N 

N 

O 

O 

O O 

N 

O O 

V O 

CH3 

O 

O 

2 H + 

N 

H 

N 

N

HOOC N 

H 

Vol. 29, 2011, No. 2: 87–102 

 

Czech J. Food Sci. 

90 

COOH HOOC NHOOC 

COOHN 

H H 


COOHN 

H H 

O 


COOHN 

COOH 

H 

HOOC 

H 

N COOH 

H 

derived from dihydroazepine, and store it in the cup 

skin. Analogously to betalamic acid involved in the 

formation of betalains, muscaflavin can spontaneously 

condense with amino acids, under the formation 

of aldimine bonds, yielding yellow hygroaurins 

(13) (Muso 1976; Li & Oberlies 2005). 

The unusually high concentration of vanadium 

in some Amanita species is ascribed to the formation 

of amavadin (14), a pale blue complex (1:2) 

of vanadium V4+ C. citrinus J.E. Lange ex P.D. Orton and C. croceus 

(Schaeff.) Gray, while in Australian fungi it forms as 

a mixture of (3R,3R', M)- (16) and (3R,3R', P)-atropoisomers. 

The green (3R)-atrochrysone (17) occurs in 

C. atrovirens Kalchbr. and C. odoratus (M.M.Moser) 

M.M.Moser, (3S)-torosachrysone-8-O-methyl ether 

in C. fulmineus (Fr.) Fr., C. citrinus J.E. Lange ex 

P.D. Orton, C. splendens R. Henry, T. equestre (L.) P. 

Kumm. and the Sulphur Knight T. sulphureum (Bull.) 

with (2S,2´S)-N-hydroxyimino- P. Kumm. (Gill & Steglich 1987; Gill 1994). A 

2,2'-dipropionic acid, isolated originally from number of anthraquinone pigments formally derived 

A. muscaria (Bayer & Kneifel 1972). 

from torosachrysone and atrochrysone by coupling 

The genus Cortinarius (Pers.) Gray (Cortina- (dimeric, trimeric and tetrameric octaketides) have 

riaceae) represents the largest genus of agarics, con- been described, mostly in Australian fungi belonging 

taining about 1000 different species in Europe and to the genera Cortinarius, Dermocybe and, to a lesser 

found worldwide together with the closely related extent, Tricholoma (Gill & Morgan 2001). 

genera Dermocybe (Fr.) Wünsche (Cortinariaceae) 

and Tricholoma (Fr.) Staude (Tricholomataceae). A 

The European members of the genus Cortinarius 

characteristically contain the xanthone dermoxan- 

range of anthraquinones and biogenetically related thone (18) and its methyl ester that were found in 

metabolites has been found in these mushrooms the stem of the Surprise Webcap C. semisanguineus 

principally due to the activity in the study of the 

Australian Cortinarius/Dermocybe species. The major 

dark orange pigment of the European toadstool 

(Fr.) Gill. These xanthones are responsible for the 

bright yellow fluorescence under UV light (Gill 

1999). The fruiting bodies of several Cortinarius 

C. cinnabarinus Fr. is fallacinol (6-O-methoxycitre- species, such as the Violet Webcap C. violaceus 

orosein, 15) (Gill & Steglich 1987; Gill 1994). (L.) Gray, have a strikingly deep violet colour 

Several species of the genera Cortinarius, Dermo- of the fruiting bodies, which is ascribes to the 

cybe and Tricholoma, such as C. cinnamomeoluteus 

P.D. Orton and T. equestre (L.) P. Kumm. (trivially 

known as Man on Horseback), produce a bright 

yellow dimeric anthraquinone flavomannin-6,6'- 

unique β-DOPA-Fe 

di-O-methyl ether (16). This pigment is biosynthesised 

by 7,7'-coupling of the corresponding green 

dihydroanthracenone (3R)-torosachrysone (17). In 

its homochiral form it also occurs in the European 

3+ complex [Fe3+ L (H O )] 2 2 2 – or 

[Fe3+ L (H O )] 4 2 2 2– 9.miraxanthinIII 10.vulgaxanthinII 11.indicaxanthin 12.muscaflavin 

 

2- 

CH3 

COOH 

O 

R + 

N CH3 

N 

O O 

O V O O 2 H 

O O 

H3C N 

N 

O 

HOOC COOH 

H 

CH3 

 

 

, where L is the (3R)-β-DOPA anion 

ligand (19). These mushrooms concentrate iron 

by as much as 100-fold over other Basidiomycota 

(Von Nussbaum et al. 1998). Unusually high concentrations 

of iron were also found in the Velvet 

Bolete, Suillus variegatus (Sw.) Kuntze (Boletales) 

(Drbal et al. 1975; Kalač et al. 1989). 

+ 

9.miraxanthinIII 10.vulgaxanthinII 11.indicaxanthin 12.muscaflavin 

 

H3CO 2- 

CH3 

COOH 

O 

R + 

N CH3 

N 

O O 

O V O O 2 H 

O O 

H3C N 

N 

O 

HOOC COOH 

H 

CH3 

 

 

 

13.hygroaurins(R=aminoacidresidue) 14.amavadin 

CH3 OCH3 O 

HO 

OH OH O 

OH OH O 

OH 

O OH OH 

OH 

OH 

H3CO CH RO 

3 

OH O OH 

CH3 

 



+ 

O 

H 

N COOH 

N 

N 

N N 

H 

H 

HO 

NH2 O 


O 

HO 

O 

OH 

COOH 

 

N 

H 13.hygroaurins(R=aminoacidresidue) 14.amavadin 

NH2 NH 

CH3 3. γ-glutamyl-4-hydroxybenzene 4. 2-hydroxy-4-iminocyclohexa-2,5-dienone 

OCH3 O 

HO 

OH OH O 

OH OH O 

H3CO OH 

O OH OH 

OH 

HOOC 

OH 

H 

COO 3CO 

CH RO 

3 

O OH O OH 

CH 

N 

3 

 

 

O 



HOOC N COOH 

- 

COO 

+ 

+ O 

N 

OH 

H 

H 

- 

COO O 

+ 

N 

N 

O 

COOH 

HOOC N COOH 

HOOC N COOH 

H 

- 

COOH 

+ 

N COO 

HOOC N COOH 

H 

- 


CONH2 + 

N COO 

HOOC N COOH 

H 

- 

+ 

N COO 

HOOC N COOH 

H 

- 

COOH 

+ 

N COO 

HOOC N 

H 

COOH 

- 

O 

HOOC N COOH 

H 

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

2- 

CH3 

COOH 

R + 

N 

O N CH3 

O O 

O V O O 2 H 

O O 

HOOC N COOH 

H 

H3C N O 

CH3 

+ 

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

H 3CO 

O 

OH O OH 

OH 

HO 

CH 3 

O OH OH 

H3CO OCH3 OH 

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

(3R)-torosachrysone, R = CH3 

OH 

O 

CH 3 

OH 

O 

RO 

OH 

OH 

O 

CH 3 

OH


H H3CO H3CO 3CO 3CO 

H3CO HOOC 

HOOC 

O 

O 

O OH 

OH 

OH O 

O 

O 

O 

O 

O 

O 

O 

O 

- 

– 

- 

- 

O 

O 

O 

- 

– 

- 

- 

O 

O 

O 

COO - 

COO 

+ 

NH3 – COO 

+ 

NH3 - 

COO 

+ 

NH3 - COO 

+ 

NH3 - 

COO 

+ 

NH3 - 

COO 

+ 

NH3 - 

+ 

NH3 Scaurins (20) are the polyene pigments with and Pholiota (Fr.) P. Kumm., where they have a 

bound glutamic acid OH that were isolated from the considerable taxonomic significance (Gill 1994). 

fruiting bodies of C. scaurus (Fr.) Fr. (Gill 1998, Hispidin is biosynthesised by two different mecha- 

2003). R Alkaloids containing the canthin-6-one nisms using the activated 4-hydroxy-6-methylpy- 

O O 

skeleton are produced by some other C. species. rone (a condensation product of three activated 

The HO parent compound canthin-6-one (21) occurs acetates) and the activated 3,4-dihydroxybenzoic 

 

in the bitter-tasting C. infractus (Pers.) Fr. together acid or from phenylalanine via a cinnamyl derivative 

with the β-carboline derivatives infractin A and that is combined with either acetate or malonate 

B (22) (Gill 1996). 

through the polyketide pathway. The related open 

The benzotropolone derivative aurantricholone chain β-keto ester (26, R = COOCH ) was isolated 

3 

(23), isolated from the bright orange-red caps some years ago as the Brick Cap H. sublateritium 

of Tricholoma aurantium (Schaeff.) Ricken, is (Schaeff.) Quél. pigment. The yellow pigment 

closely related to the naphthalenoid pulvinic acid hispolon is the hydrolytic and decarboxylation 

badione A occurring in the Boletales mushrooms product of the open chain β-keto ester (26) (Gill 

(see Chapter 2). It occurs naturally as a metal 1994). It also occurs in mushrooms of the Hy- 

chelate; the predominant counter ion is calcium menochaetaceae family, e.g. in several Inonotus 

(Klostermeyer et al. 2000). Minor pigments are P. Karst., Onnia P. Karsten and Phellinus Quél. 

the yellow aurantricholides A and B (24). species. (Lee & Yun 2006) 

The yellow-brown styrylpyrone pigments bis- Orange-yellow polyenes of fatty acid origin, 

noryangonin and hispidin (25) are widespread dihydroxerulin, xerulin and xerulinic acid (27), 

among fungi of the Strophariaceae family, genera are the pigments of Oudemansiella melanotricha 

Gymnopilus P. Karst., Hypholoma (Fr.) P. Kumm. (Dörfelt) M.M. Moser (Oudemansiella Speg., 

HO 

OH 

NO2 COOH 

OH O 

H 

R 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 

25.bisnoryangonin,R=H26.hispolon,R=CH327.dihydroxerulin,R=CH2CH2CH328.stephanosporin 

hispidin,R=OHxerulin,R=CH=CHCH3 

xerulinicacid,R=CH=CHCOOH 

NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 

29.mycearubinA 30.mycearubinB 31.sanguinoneA,R=H 32.haematopodin,X=O 

sanguinoneB,R=CH3 haematopodinB,X=NH 

O 

HO 

OH 

NO2 COOH 

OH O 

H 

R 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



O 

HO 

OH 

NO2 COOH 

OH O 

R 

H 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



O 

HO 

OH 

NO2 COOH 

OH O 

R 

H 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



O 

HO 

OH 

NO2 COOH 

OH O 

R 

H 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



O 

HO 

NO2 COOH 

OH O 

H 

HO 

R 

O 

N 

HOOC O OH O 

N Cl 

H 

O 

O OH 

O 

COO 

 

 


H3CO O 

 



NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



O 

- 

HOOC 

- 

O OH O 

O 

O COOH 

H 

R 

- 

N COOH 

O O 

COO H 

H + 

3CO O 

NH3 HO 

 

 

 

18.dermoxanthone 19.DOPAanion 20.scaurinA,R=H 

scaurinB,R=OH 

OH O 

OH 

HO 

O O 

R 

O 

O 

N 

HO 

H 

OH 

R O 

N 

O 

O 

COOCH3 HO 

O 

 

 

 

 

21.canthin6one 22.infractinA,R=H 23.aurantricholone 24.aurantricholideA,R=OH 

infractinB,R=OH aurantricholideB,R=H 

- 

HOOC 

- 

O OH O O 

O COOH 

H 

R 

- 

N COOH 

O O 

COO H 

H + 

3CO O 

NH3 HO 

 

 


scaurinB,R=OH 

OH O 

OH 

HO 

O O 

R 

O 

O 

N 

HO 

H 

OH 

R O 

N 

O 

O 

COOCH3 HO 

O 

 

 

 

 



- 

HOOC 

- 

O OH O 

O 

O COOH 

H 

R 

- 

N COOH 

O 

O 

COO H 

H + 

3CO O 

NH3 HO 

 

18. dermoxanthone 19. β-DOPA anion 20. scaurin A, R = H 

scaurin B, R = OH 

OH O 

OH 

HO 

O O 

R 

O 

O 

N 

HO 

H 

OH 

R O 

N 

O 

O 

COOCH3 HO 

O 

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

infractin B, R = OH aurantricholide B, R = H 

- 

- 

O 

O COOH 

H 

R 

- 

N COOH 

O 

H 

+ 

NH3 HO 

 

 


scaurinB,R=OH 

OH O 

OH 

HO 

O O 

R 

O 

O 

N 

HO 

H 

OH 

R O 

N 

O 

O 

COOCH3 HO 

O 

 

 

 

 



R 

R 

R 

18.dermoxanthone 18.dermoxanthone 18.dermoxanthone 18.dermoxanthone 18.dermoxanthone 18.dermoxanthone 19.DOPAanion 19.DOPAanion 19.DOPAanion 19. 19.DOPAanion 19.DOPAanion 19.DOPAanion β-DOPA anion 

20.scaurinA,R=H 






scaurinB,R=OH 

scaurinB,R=OH 

scaurinB,R=OH 

scaurinB,R=OH 

scaurinB,R=OH 

scaurinB,R=OH 

N 

N 

N 

O 

O 

O 

 

R 

R 

R 

 

 

 

N 

N 

N 

H 

H 

H 

COOCH COOCH 3 

3 

3 

 

HO 

HO 

HO 

 

 

 

OH 

OH 

OH O 

O 

O 

OH 

OH 

OH 

HO 

HO 

HO 

O 

O 

O 

O 

O 

O 

OH 

OH 

OH 

O 

O 

O 

O 

O 

O 

HO 

HO 

HO 

R 

R 

R 

HO 

HO 

HO 

 

O 

O 

O COOH 

COOH 

H 

H 

H 

N 

N 

N COOH 

COOH 

H 

H 

H 

O 

O 

O 

O 

O 

O 

O 

O 

O 

 

 

 

21.canthin6one 21.canthin6one 21.canthin6one 21.canthin6one 21.canthin6one 21.canthin6one 22.infractinA,R=H 22.infractinA,R=H 22.infractinA,R=H 22.infractinA,R=H 22.infractinA,R=H 22.infractinA,R=H 23.aurantricholone 23.aurantricholone 23.aurantricholone 23.aurantricholone 23.aurantricholone 23.aurantricholone 24.aurantricholideA,R=OH 

24.aurantricholideA,R=OH 





infractinB,R=OH infractinB,R=OH infractinB,R=OH infractinB,R=OH infractinB,R=OH infractinB,R=OH aurantricholideB,R=H 

aurantricholideB,R=H 





R 

R 

R 

R 

HO 

O 

O 

O 

OH 

R 

R 

R 

O O 

 

H H3C H3C 3C 

H3C H H3C H3C 3C 

H3C O 

O 

O 

O O 

O O 

O 

O 

O 

O O 

O 

O OH 

OH 

OH 

O 

O 

O 

O 

O 

O 

H H3C H3C 3C 

H3C O 

O 

O 

OH 

OH 

OH 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

O 

HO 

HO 

HO 

O 

O 

O 

OH 

OH 

OH 

O 

O 

O 

OH 

OH 

OH 

CH CH 3 

CH 3 

3 

R 

R 

R 

HO 

HO 

HO 

O 

O 

O 

 

 

 

 

 

 

 

33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H 34.leucomentin2 34.leucomentin2 34.leucomentin2 34.leucomentin2 34.leucomentin2 34.leucomentin2 35.flavomentinA 

35.flavomentinA 





atromentin,R=OH 






HO 

R 

HO 

OH 

HO 

O O 

 

R 

OH O 

R 

 

NO2 COOH 

H 

O 

N 

N Cl 

H 

O 

O OH 

 

 




NH2 NH2 HO 

R R 

HO HO 

OH OH 

HO HO 

O O O O 

HO 

 

R R 

OH OH O O 

R R 

 

NO NO 2 2 

COOH 

H H 

O O 

N N 

N N Cl Cl 

H H 

O O 

O O OH OH 

 

 


25. bisnoryangonin, R = H 26. hispolon, R = CH3 27. dihydroxerulin, R = CH2-CH2-CH3 28. stephanosporin 


hispidin, R = OH xerulin, R = CH=CH-CH3 


xerulinic acid, R = CH=CH- COOH 

NH NH 2 2 

NH NH 2 2 

HO 

HO 

R 

OH O 

R 

 

NO2 COOH 

H 

O 

N 

N Cl 

H 

O 

O OH 

 

 




NH2 NH2 NN 

N N 

COOH 

COOH 

OO 

O O 

OO 

O O 

NN 

N N 

COOH 

COOH 

NH NH 

NH 

HOOC 

HOOC 

HH 

H H 

NN 

N N 

NH NH 

NH 

OO 

O O 

HHN 

HNH 

NN 

 

 

 

HH 

H H 

91

R 

HO 

RR 

R 

HO HO HO 














HOOC 

- - 

HOOC OO 

OH OH 

- 

O OH O OO 

O OO 

O OO 

COOH 

COOH 

NH2 NH NH 2NH 

2 2 

H3CO H3CO H3CO COOH COOH 

O OO 

Physalacriaceae) that act as inhibitors H of choles- of theOH mushroom decomposing O OO 

O 

H under the influence 

3C HH3CH R O 

N 

3C 3C 

terol biosynthesis (Kuhnt et al. 1990). H3C H3C H3CH 3C of air and light (Hopmann & Steglich 2006). O 

The carrot O 

COOCH truffle, Stephanospora caroticolor 3 O 

O O 

OO 

O 

HO 

O 

 

O O 

O O 

O O OH OH OH OH 

(Berk.) Pat. (Stephanospora H3C Pat., HH H Stephanospo- 

O OO 

O 

3C 3C 3C 

21.canthin6one 22.infractinA,R=H 23.aurantricholone O OO 

O24.aurantricholideA,R=OH 

raceae), contains in its subterranean tuber-like 

2 Boletales 

infractinB,R=OH 

fruiting bodies the R pigment RR 

R stephanosporin O OO 

(28). O aurantricholideB,R=H 

OO 

OH O OH OH OH 

O OO 

O 

O OO 

O 

O OO 

O 

This unusual hydrazine derivative is biosynthesised 

O 

Mushrooms of the order Boletales are charac- 

OO 

O 

O OO 

O 

using 2-chloro-4-nitrophenol as the building block. terised by a diversity HO HO HO HOof 

colours O OOmainly 

O derived 

OH 

Both compounds occur naturally as their potas- OH OH OH OH from terphenylquinones and pulvinic acids. Tersium 

salts O and OO 

Oare 

responsible for the bright OHorange 

OH OH OH phenylquinones, exemplified by polyporic CH3 CH CH3 CH 3acid 

3 

R RR 

R 

R 

HO HO HO HO 

O OO 

O 

colour of the mushroom O (Lang O 

et al. 2001). (33) and atromentin 

(33), are mainly produced by 

33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H The pyrroloquinone alkaloids 34.leucomentin2 isolated 34.leucomentin2 34.leucomentin2 34.leucomentin2 from My- wood-rotting higher 35.flavomentinA 

fungi 35.flavomentinA 



of the order Polyporales 

HO 




cena atromentin,R=OH 

(Pers.) Roussel (Mycenaceae) species include growing on various deciduous trees but in other 

the red pigments mycearubin A (29), mycearubin B higher fungi, such as in the Boletales fungi, they 

(30) and related compounds from the fruiting bod- only appear sporadically. However, atromentin 

ies of M. rosea (Schumach.) Gramberg (Peters & is their key intermediate for many conversions 

Spiteller 2007a) and the Bleeding Fairy Helmet leading to more highly hydroxylated terphenyl- 

M. haematopus (Pers.) P. Kumm. The blue sanquinones, hydroxypulvinic acids, cyclopentenones 

guinones A and B (31) were isolated from M. san- and related compounds. In the intact fruit bodies, 

guinolenta (Alb. & Schwein.) P. Kumm. (Peters atromentin occurs in the form of its colourless 

& Spiteller 2007b) and red haematopodins from precursors leucomentins. 

the fragile reddish-brown stems of M. haematopus Leucoderivative of atromentin esterified with 

(Hopmann & Steglich 2006; Peters et al. 2008). (2Z,4S,5S)-4,5-epoxyhex-2-enoic acid from the 

These alkaloids are exemplified by the minor pigment lignicolous fungi Tapinella atrotomentosa (Batsch) 

haematopodin (32), a breakdown product of the labile Šutara (Tapinella E.-J. Gilbert, Tapinellaceae) spo- 

red haematopodin B (32), which is the main pigment rophore is leucomentin-2 (34) (Gill & Steglich 

1987; Gill 1994; Liu 2006; Hanson 2008b). This 

HO 

H 

OH 

R O 

N 

O 

O 

COOCH3 HO 

O 

 

 

 

 



R 

OH 

NO2 COOH 

OH O 

R 

H 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



HO 

H 

OH 

R O 

N 

O 

O 

COOCH3 HO 

O 

 

 

 

 



R 

OH 

NO2 COOH 

OH O 

H 

R 

HO 

O O 

R 

O 

N 

N Cl 

H 

HO 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



HO 

R 

NO2 COOH 

OH O 

H 

HO 

R 

O 

N 

N Cl 

H 

O 

O OH 

 

 

 




NH NH 

2 

2 

COOH 

COOH 

HOOC 

O 

N 

N 

N 

HN 

O 

O 

H 

NH 

H 

NH 

NH 

N 

HN 

O 

HN 

N 

X N O 

N O 

O 

O 

COOH 

R 

 

 

 

 



92 

O 

HO HO HO HO 

O 

O O OO 

O 

HO 

HO 

HO 

HO 

R 

 

RR 

R 

 

O NH2 NH NH 2NH 

2 2 COO 

 

COOH COOH 

HOOC HOOC 

HOOC 

- 

O 

- 

O 

COO 

R 

 

+ 

NH3 HO 

 

- 

O 

- 

O 

COO 

R 

 

+ 

NH3 HO 

 

- 

- 

O 

R 

+ 

NH3 HO 

 

 

O OO 

O N NN 

N 

N NN 

N Cl Cl Cl Cl 

H HH 

H 

O OO 

O 

O OO O OH OH OH OH 

 

 

N NN 

COOH 

COOH 

H HH 

O 

O O O 

N 

N 

N 

HN 

N 

N 

N 

H 

N 

N 

N 

HN 

N 

N 18.dermoxanthone 18.dermoxanthone 18.dermoxanthone O 

19.DOPAanion 19.DOPAanion 19.DOPAanion N 

N 20.scaurinA,R=H 


20.scaurinA,R=H HN 

O OO 

O 

scaurinB,R=OH 

scaurinB,R=OH 

scaurinB,R=OH 

O OO 

O 

H HH 

H NH NH NH NH 

H HH 

H 

NH NH NH 

NH 

HN NH 

NH NH NH 

N 

HN 

N 

HN 

O O 

HN HN NN 

HN HN 

O 

HN 

N NN 

N 

OH OH OH O OO 

X X X N ON 

N O O 

N NON 

NOHO 

OH OOH 

X N O 

O 

O OO 

O 

O OO 

O HO HO HO 

COOH COOH 

R RR 

R 

 

 

 

 

29.mycearubinA 29.mycearubinA 29.mycearubinA 29.mycearubinA 

30.mycearubinB 30.mycearubinB 30.mycearubinB 30.mycearubinB 31.sanguinoneA,R=H 31.sanguinoneA,R=H 31.sanguinoneA,R=H 31.sanguinoneA,R=H 

O OO 

O OO 

R 

32.haematopodin,X=O 

R R 




sanguinoneB,R=CH3 sanguinoneB,R=CH3 sanguinoneB,R=CH3 sanguinoneB,R=CH3 O OO 

haematopodinB,X=NH 




O OO 

N NN 

HO HO HO 

R RR 

O OO 

O OO 

R RR 

 

O OO 

H3C H3C H3C HO HO HO 

O OO 

O OO 

O OO 

O OO 

H3C H3C H3C OH OH OH 

O OO 

OH OH OH 

OH OH OH 

 

 

 

O OO 

H3C H3C H3C HO HO HO 

O OO 

O OO 

O OO 

O OO 

O OO 

H HH 

O OO 

OH OH OH 

CH CH 3CH3 

3 

O OO 

33.polyporicacid,R=H 33.polyporicacid,R=H 33.polyporicacid,R=H 




34.leucomentin2 34.leucomentin2 34.leucomentin2 35.flavomentinA 


35.flavomentinA


HO 

HO 

compound and leucomentin-3, R -4, -5 and -6 were quinone ring has been oxidized and opened. The 

found in a number O OHof 

other fungi. Mushrooms of unsubstituted parent compound, pulvinic acid, 

OH 

the genus R Tapinella also produce small amounts of only occurs in the form of its methyl ester named 

orange-yellow flavomentins A-DR and violet spiro- vulpinic acid. Xerocomic and variegatic acids play 

O 

mentins HO A-D (spiromentins E-J, derivatives of ben- the most important role being responsible for 

O 

zene-1,2,4,5-tetraol, are colourless) derived from the blue colours acquired in many boletes after 

atromentin. The flavomentins constitute diesters their fruiting bodies are injured, which results in 

and monoesters of atromentin with (2Z,4S,5S)-4,5- the oxidation of these acids to the corresponding 

epoxyhex-2-enoic and (2Z,4E)-hexa-2,4-dienoic blue chinonmethid anions (40). Pulvinic acids are 

acids. The spiromentins possess a unique spiro especially widespread in mushrooms belonging to 

structure in which a 4,5-dihydroxybenzo-1,2- the Gomphidiaceae and Suillaceae families, to the 

quinone is linked to a lactone acetal unit (Besl genera Gomphidius Fr. and Suillus Gary. The yellow 

et al. 1989). Flavomentin A (35) and spiromentin pigment gomphidic acid (39) was found for the first 

A (36) exemplify these metabolites. 

time in the Slimy Spike-cap G. glutinosus (Schaeff. 

Simple oxidation products of terphenylquinones ex Fr.) Fr. (Knight & Pattenden 1976). 

under the preservation of the central quinone The yellow-brown cap and stem of the Larch 

ring include cycloleucomelone (37) and cyclova- Bolete Suillus grevillei (Klotzsch) Sing. contain at 

riegatin (37), which is the precursor of the violet least 11 yellow, orange and red pigments derived 

thelephoric acid (38). Cycloleucomelone OH 

O 

occurs from decarboxylated OH 

pulvinic acids, of which 3',4',4- OH 

in the fruiting bodies O of Boletopsis leucomelaena trihydroxypulvinone OH (41) is the major pigment 

O 

O 

(Pers.) Fayod (Boletopsis Henn., Suillaceae) (Jägers (Besl & Bresinsky 1997). Cyclovariegatin (37) 

HO 

et al. 1987) and is accompanied O by a series of is also partly responsible for its colour O (Edwards 

colourless analogues O containing five, four and & Gill O 1973). 

O 

HO 

O 

three acetyl residues. Cyclovariegatin occurs in In the pathway leading to atromentin, instead of 

O 

O 

this mushroom as the colourless peracetate HO of the two C-C bonds only one C-C HO bond may be formed. 

CH R 

3 

OH 

leucoform (Edwards & Gill 1973). 

The resulting lactonisation then yields grevil- 

The major pigments of the order Boletales are lins (42). Grevillins A, B, C and D are a group of 

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

the yellow pulvinic acids (39) that are formed cyclovariegatin, characteristic R = OH orange to red 2H-pyran-2,5(6H)dione 

through lactone formation, after the terphenyl- pigments that occur only in the fruiting body of 

1 

2 

O 

OH 

3 

O 

O 

 

- 

O O 

HO 

- 

O 

O 

R 

 

39.atromenticacid,R1=R2=R3=H 40.chinonmethidanionofxerocomicacid,R=H 

xerocomicacid,R1=H,R2=OH,R3=H chinonmethidanionofvariegaticacid,R=OH 

gomphidicacid,R1=H,R2=R3=OH isoxerocomicacid,R1=OH,R2=R3=H variegaticacid,R1=OH,R2=OH,R3 R 

O OH 

OH 

R 

R 

O 

HO 

O 

=H 

3 

2 

R R 

OH 

O 

OH 

HO 

OH 

1 

HO 

R 

O 

O 

O 

O 

HO OH 

O 

4 

HO 

O 

R O 

O 

 

 

 

41.3,4,4trihydroxypulvinone 42.grevillinA 43.gomphilactone 

grevillinB 

grevillinC 

grevillinD 

O 

O 

O 

O 

O 

HO 

HO 

O 

O 

O 

O 

HO 

O 

O 

HO 

HO HO 

O 

1 

2 

O 

OH 

3 

O 

O 

 

- 

O O 

HO 

- 

O 

O 

R 

 



gomphidicacid,R1=H,R2=R3=OH isoxerocomicacid,R1=OH,R2=R3=H variegaticacid,R1=OH,R2=OH,R3 R 

O OH 

OH 

R 

R 

O 

HO 

O 

=H 

3 

2 

R R 

OH 

O 

OH 

HO 

OH 

1 

HO 

R 

O 

O 

O 

O 

HO OH 

O 

4 

HO 

O 

R O 

O 

 

 

 


grevillinB 

grevillinC 

grevillinD 

O 

O 

O 

O 

O 

HO 

HO 

O 

O 

O 

O 

HO 

O 

O 

HO 

HO HO 

O 

1 

2 

O 

OH 

3 

O 

O 

 

- 

O O 

HO 

- 

O 

O 

R 

 



gomphidicacid,R1=H,R2=R3=OH isoxerocomicacid,R1=OH,R2=R3=H variegaticacid,R1=OH,R2=OH,R3=H 3 

2 

R R 

OH 

O 

OH 

HO 

OH 

1 

HO 

R 

O 

O 

O 

O 

HO OH 

O 

4 

HO 

O 

R O 

O 

 

 

 


grevillinB 

grevillinC 

grevillinD 

O 

O 

O 

O 

O 

HO 

HO 

O 

O 

O 

O 

HO 

O 

O 

HO 

HO HO 

O 

R 

O OH 

OH 

R 

R 

O 

HO 

O 

1 

2 

OH 

3 

O 

O 

O 

– 

HO 

O O – 

R 

O 

O 

39. atromentic acid, R1 = R2 = R3 = H 40. chinonmethid anion of xerocomic acid, R = H 

xerocomic acid, R1 = H, R2 = OH, R3 = H 

gomphidic acid, R 

chinonmethid anion of variegatic acid, R = OH 

1 = H, R2 = R3 = OH 

isoxerocomic acid, R1 = OH, R2 = R3 = H 

variegatic acid, R1 = OH, R2 = OH, R3 OH OH 

OH OH 

O O 

O O 

HOOC HOOC HOOC HOOC 

R R 

O O 

HO HO 

O O 

OH OH 

OH OH 

 

44.xerocomorubin,R=H 44.xerocomorubin,R=H 44.xerocomorubin,R=H 45.badioneA 45.badioneA 45.badioneA 

O O 

HOOC HOOC HOOC HOOC 

OH OH 

OH OH 

 

46.norbadioneA 



variegatorubin,R=OH 



= H 

HO 

HO 

O 

O 

O 

O 

O 

O O 

O O 

CH 3 CH3 O 

O 

OH 

O 

OH OH 

 

 

OH 

HO 

HO 

R 

HO 

R 

O 

O 

HO OH 

R 

4 

O 

HO 

O 

36.spiromentinA 36.spiromentinA 36.spiromentinA 37.cycloleucomelone,R=H 37.cycloleucomelone,R=H 37.cycloleucomelone,R=H 

cyclovariegatin,R=OH 



38.thelephoricacid 



O 

O 

OH OH 

O 

O 

O 

R 

3 

OH OH 

 

R 

R 

2 

1 

 

HO 

HO 

HO 

O 

OH OH 

OH 

O 

O 

O 

O 

O 

O 

O 

O 

OH OH 

O 

O 

O 

OH OH 

 

93 

OH 

 

OH OH


mushrooms belonging to the genus Suillus Gray. 

S. grevillei (Klotzsch) Sing. and S. luteus (L. ex Fr.) 

S. F. (Slippery Jack) contain grevillins A, B and C, 

S. granulatus (L. ex Fr.) O. Kuntze (Weeping Bolete) 

contains grevillins B, C and D, of which the major 

pigment is grevillin D (Besl et al. 1974). 

The colourless, but easily oxidisable 1,2,4-trihydroxybenzene 

and its derivatives commonly 

occur in mushrooms belonging to the Gomphidiaceae 

family and to the genus Suillus Gray. The 

oxidation products of 1,2,4-trihydroxybenzene 

include the red gomphilactone (43) and the corresponding 

biphenyls. Variegatorubin (44) and 

xerocomorubin (44) exemplify the red pigments 

formed from pulvinic acids by the second lactone 

ring production (Besl & Bresinsky 1997). 

High concentrations of radionuclides occurring in 

the fruiting bodies of the Bay Bolete Boletus badius 

(Fr.) Fr. (Boletus Fr., Boletaceae) after the nuclear reactor 

accident at Chernobyl have been ascribed to the 

complexation of 137 

CH R 

3 

 

Norbadione A (46) is the dominating compound 

OH 

in the dying mushroom Pisolithus arrhizus (Scop.) 

36.spiromentinA 37.cycloleucomelone,R=H Rauschert (Pisolithus 38.thelephoricacid 

Alb. & Schwein, Scleroder- 

cyclovariegatin,R=OH mataceae) where it occurs in amount of over 25% 

of the dry weight of the fungus. Badione A (45) and 

several similar compounds are minor components 

R 

O OH 

(Winner et al. 2004). 

OH 

Oxidative coupling of two molecules of xerocomic 

R 

R 

acid (39) yields bright yellow sclerocitrin (47) oc- 

O 

curring in the fruiting bodies of the common Earth 

HO 

O 

Ball Scleroderma citrinum Pers. (Scleroderma Pers., 

Sclerodermataceae) together with norbadione A 

(46) as the main pigments, which are accompanied 

by xerocomic acid (39) and badione A (45) 


Sclerocitrin is the main pigment of the lemonyellow 

coloured stalk base of the Peppery Bolete 

Cs by the so called naphthalenoid 

pulvinic acids that occur as their potassium salts in 

the cap skin of this toadstool. The main compounds 

Chalciporus piperatus (Bull.) Bataille (Chalciporus 

Bataille, Boletaceae). It is accompanied by the second 

yellow pigment chalcitrin (48), norbadione A 

(46), variegatic acid (39) and variegatorubin (44) 


The decarboxylation products of pulvinic acids, 

are badione A (45) and norbadione A (46) that are 2,5-diarylcyclopentenones, appear in fungi almost as 

responsible for the chocolate brown and golden frequently as terphenylquinones. Typical examples 

yellow colours of cap skin of this bolete and related are chamonixin (49), involutin (49) and the more 

bolete species (Aumann et al. 1989). 

highly oxidised gyrocyanin (50) and gyroporin (50). 

1 

2 

O 

OH 

3 

O 

O 

 

- 

O O 

HO 

- 

O 

O 

R 

 



gomphidicacid,R1=H,R2=R3=OH isoxerocomicacid,R1=OH,R2=R3=H variegaticacid,R1=OH,R2=OH,R3=H O 

OH 

OH 

HO 

O 

O 

HO 

4 

HO 

O 

R O 

 

3 

2 

R R 

OH 

HO 

1 

R 

O 

O 

OH 

O 

O 

 

 


grevillinB 

grevillinC 

grevillinD 

94 

OH 

OH 

HO 

O 

HO 

O 

 

41.3,4,4trihydroxypulvinone 

3 

2 

R R 

O 

1 

R 

O 

HO OH 

4 

R O 

 

42.grevillinA,R 

OH 

HO 

O 

O 

O 

O 

1=R3=R4=H,R2=OH 43.gomphilactone 

grevillinB,R1=R3=H,R2=R4=OH grevillinC,R1=R2=R4=OH,R3=H grevillinD,R1=R3=R4=OH,R2 OH 

O 

O 

OH 

OH 

O 

OH 

O 

O 

HO 

O 

HO 

O 

O 

O 

=H 

O 

HO 

O 

HO 

O 

HO 

O 

OH 

O 

O 

OH 

O 

OH 

R 

 

HO 

HOOC 

O 

O 

O 

O 

HO 

O 

HO 

OH 

HOOC 

O 

O 

OH 

 

HO 

O 

HO O 

HO 

44.xerocomorubin,R=H 45.badioneA 46.norbadioneA 


HOOC 

OH 

O 

O 

HOOC 

O 

O 

 

OH 

OH


HO 

O 

O 

O 

O HO 

O 

H 

O 

OH 

COOH 

H 

HO 

HOOC 

O 

O 

OH 

 

HO 

HOOC 

OH 

COOH 

OH 

H 

HO O 

47.sclerocitrin 48.chalcitrin 

They occur e.g. in several HOfamilies OHof 

Boletales, in the 

R 

genera Chamonixia Rolland (Boletaceae), Gyrodon 

Opat. (Paxillaceae), Gyroporus Quél. (Gyroporaceae), 

HO OH HO 

Leccinum Gray (Boletaceae), O Melanogaster Corda 

 

(Melanogasteraceae), Paxillus Fr. (Paxillaceae) and 

that HO occurs O in S. granulatus (L. exO Fr.) O. O Kuntze. 

Its oxidation R products are responsible for the caps’ 

brown colour. Prenylated benzoquinones, corre- 

OH HO 

O 

sponding O to 1,2,4-trihydroxybenzene O(mentioned 

above), mostly appear as meroterpenoids named 

several other families and genera. The pigments are boviquinones. Boviquinone-3 (2,5-dihydroxyresponsible 

for the conspicuous deep brown and 3-farnesyl-1,4-benzoquinone) is biosynthesised 

bright blue colour reactions observed when the 

fruiting bodies of mushrooms are bruised. Involutin 

by Chroogogompus rutilus (Schaeff.) O.K. Mill., 

Chroogomphus (Singer) O.K. Mill. (Gomphi- 

occurs in P. involutus (Batsch ex Fr.) Fr. (chamonixin diaceae), bovinoquinone-4 (2,5-dihydroxy-3-gera- 

is a minor compound); chamonixin is a constituent nylgeranyl-1,4-benzoquinone, 53) is an example of 

in C. caespitosa Rolland and gyrocyanin in G. cya- prenylated benzoquinones found in Suillus bovinus 

nescens (Bull. ex Fr.) Quél. The colour changes of the (L.) Roussel. (Mühlbauer et al. 1998). The red 

latter mushroom are associated with the related me- pigment tridentoquinone (54) is the main pigment 

tabolite of gyrocyanin, which is oxidised to the blue of S. tridenticus (Bres.) Singer, which is related 

anion (51) (Feling et al. 2001; Hanson 2008b). to the linear boviquinone-4 (53) from S. bovinus 

The prenylated compounds occur only rarely (L.) Roussel. In the mushroom, tridentoquinone 

in Boletales being biosynthesised from 3,4-dihy- is accompanied by several compounds of similar 

droxybenzoic acid (Besl & Bresinsky 1997). The structure (Lang et al. 2008). Mushrooms of the 

aromatic ring often bears an additional farnesyl genus Rhizopogon Fr. (i.e. Rhizopogon pumilionum 

or geranylgeranyl side-chain derived from the (Ade) Bataille), closely related to the genus Suil- 

terpenoid pathway. Suillin (52) is an example of lus Gray, contain rhizopogone (55) as the main 

acetylated and prenylated 1,2,4-trihydroxybenzene pigment (Lang et al. 2009). 

- 

 

49.chamonixin,R=H 50.gyrocyanin,R=H 51.blueanionofgyrocyanin 

involutin,R=OH gyroporin,R=OH 

OH 

OH 

O 

CH3 O 

COOH 

COOH 

OH 

H3C O CH3 CH3 CH3 CH 

OH 

3 

O 

OH 

O 

O 

OH 

O 

H 

O 

O HO 

H 

OHO 

HO 

HO 

O 

O 

H 

H 

H 

H 

52.suillin 

O H 

O H 

H 

H 

O 

O O 

O 

HO O 

HO O 

O 

HO O 

HO 

H3C CH3 CH 

O 

O HOOC 

HOOC 

HOOC 

CH CH 

O 3 

3 

3 

H CH3 CH 

3C 3 

O 

OH O 

OH 

O 

H 

O 

CH 

OH 

3 

OH OH 

H3C OH 

CH3 OH 

COOH 

COOH 

H 

HO 

3C O 

HO 

OH 

HO 

HO 

OH 

O CH 

O CH 

3 

3 

O CH3 

 

 

47.sclerocitrin 

47. sclerocitrin 

48.chalcitrin 

48. chalcitrin 

53.boviquinone4 54.tridentoquinone 55.rhizopogone 

HO OH 

R 

HO OH 

HO 

R 

O 

R 

HO O 

O 

R 

O 

O O 

HO 

O 

H 

O 

OH 

 

HO 

O 

OH 

O 

 

HO 

O 

O 

H3COOC N CH3 H 

CH3 

- 

HO 

O 

OH HO 

O 

OH HO 

 

O 

O 

49.chamonixin,R=H 50.gyrocyanin,R=H 51.blueanionofgyrocyanin 

involutin,R=OH gyroporin,R=OH 

- 

49. chamonixin, R = H 50. gyrocyanin, R = H 51. blue anion of gyrocya 

involutin, R = OH gyroporin, R = OH 

H 3C 

O 

OH 

O 

56.melanocrocin 

OH 

OH 

OH 

O 

CH 

CH 3 

3 H3C H CH3 CH 

3C CH3 3 

H 

CH 3C O CH 

3 CH3 CH 3 CH 

3 CH 3 CH3 CH3 3 

O 

CH 3 

O 

52.suillin 

57.canthaxanthin 

CH 3 

52. suillin 

CH 3 

H 3 C CH 3 

H 

H3C CH3 CH 3C CH 

CH 

CH CH 

3 

3 CH 3 CH3 3 

3 

3 

O 

O H3C O 

O 

H 

CH H 

CH 3 

OH 

3 

OH 

H3C OH H3C OH 

CH3 H C 

O 

 

O 

H 

H 

OH 

O 

 

CH3 O 

OH 

CH H3C 3 

95 

CH 3 

CH3 O 

O

Vol. 29, 2011, No. 2: 87–102 


Melanocrocin (56) is a unique brilliant yellow Karst., the polypore with a red-brown fruiting 

HO 

OH 

polyene pigment, with bound phenylalanine, iso- body (Bu’Lock et al. 1962), where it is accompalated 

from theOsubterranean fungus Melanogaster O 

H 

47. sclerocitrin nied by bisnoryangonin 48. chalcitrin (25), hypholomin B (58) 

broomeianus H that resemble truffles (Aulinger 

3COOC N CH and 3 the yellow pigment hispolon (26, R = CH ) 3 

et al. 2001). H 

HO OH 

CH (Ali et al. HO 1996). These O pigments also occur O in O 

3 

R 

several mushrooms R of the Hymenochaetaceae 

56.melanocrocin 

HO OH family, HO e.g. in Inonotus P. Karst., OH Onnia HO P. Karsten 

O 

3 Cantharellales O 

and Phellinus Quél. O species and in the genus Hy- O 

O 

pholoma (Fr.) P. Kumm. of the Strophariaceae 

H3C Carotenoids H CH are 3 not widespread CH in higher fungi as 

3C CH3 3 

family (Agaricales). Inoscavin A, reported to be 

they are in plants; nevertheless, they were isolated a free radical scavenger, isolated from the fruit- 

from several yellow pigmented Cantharellus CH Juss. ing bodies of the mushroom P. xeranticus (Berk.) 

3 CH H 

3 3C CH3 CH (Cantharellaceae) 3 species. The Golden Chanterelle Pegler (Phellinus, Hymenochaetaceae) has been 

O 

C. cibarius Fr. pigment mixture was found to consist assigned the fused styrylpyrone structure (59), 

mainly of β-carotene57.canthaxanthin and also present were lycopene, which relates inoscavin A closely to hispidin (25) 

α-carotene and two other carotenes, probably the and thence to hypholomin B (58). 

γ- and δ-isomers or the xanthophyl canthaxanthin 

(57) that was found in the pink to red-orange Cinnabar 

Chanterelle C. cinnabarinus (Schwein.) Schwein. 

as the main pigment (Haxo 1950; Hanson 

5 Polyporales 

2008b). 

4 Hymenochaetales 

Styrylpyrone hispidin (25) was originally isolated 

Species within the order Polyporales are saprotrophic 

and most of them wood-rotters. The Polyporaceae 

are a family of such wood-decay fungi that 

contain pigments mostly derived from polyporic 

acids and terphenylquinones. The dark red polyporic 

acid (33), the parent compound of numerous 

as the main constituent of the plant pathogen 

the Chaga Fungus Inonotus hispidus (Bull.) P. 

terphenylquinones and related compounds, is the 

major component of Hapalopilus nidulans (Fr.) 

- 

HO 

OH 

47. sclerocitrin 48. chalcitrin 

HO OH 

HO O 

O O 

R 

R 

HO OH HO OH HO 

O 

O 

O 

O 

49. chamonixin, R = H 50. gyrocyanin, R = H 51. blue anion of gyrocyani 


OH 

OH 

CH3 H3C O CH3 CH3 CH3 CH3 O 

52. suillin 

H3C CH3 CH3 O 

CH3 OH 

HO 

O CH3 CH3 CH3 H CH 

3C 3 

O 

H 

O 

H3C OH 

CH3 H3C O 

HO 

O CH3 O 

C 

OH 

53. boviquinone-4 54. tridentoquinone 55. rhizopog 

- 

49. chamonixin, R = H 50. gyrocyanin, R = H 51. blue anion of gyrocyani 


OH 

OH 

CH3 H3C O CH3 CH3 CH3 CH3 O 

52. suillin 

H3C CH3 CH3 O 

CH3 OH 

HO 

O CH3 CH3 CH3 H CH 

3C 3 

O 

H 

O 

H3C OH 

CH3 H3C O 

HO 

O CH3 O 

C 

OH 

53. boviquinone-4 54. tridentoquinone 55. rhizopog 

96 

H 3C 

O 

O 

CH 3 CH 3 CH 3 CH 3 

CH 3 

52.suillin 

H3C CH3 CH3 O 

CH3 OH 

HO 

O CH3 

53.boviquinone4 

O 

O 

O 

O 

O 

O HOO 

CH3 CH HO 

O 3 

HO 

H3C O O 

HO 

H 

H 

O 

H3C OH 

H H 

O 

O H 

HO 

H3C HO 

O 

O 

O 

HO 

HO 

O HOOC O CH 

HOOC 

3 

O HOOC 

HOOC 

OH 

OH 

OH 

54.tridentoquinone OH 

COOH 

COOH 

O 

COOH 

O 

OH 

COOHOH 

O 

OH 

OH H 

O 

CH H 

3 CH3 O H 

CH O H H 

3 

OH 

O H 

O 

HO 

O 

O CH3 

55.rhizopogone 

H3COOC H3COOC H3C CH3 H3C CH3 O 

O 

O 

H 

O 

HN 

NH H 

56. melanocrocin 

56. melanocrocin 

O 

O 

CH3 

CH CH3 

3 

CH3 CH3 CH3 CH3 CH3 CH3 CH3 57. canthaxanthin 

57. canthaxanthin 

CH3 CH3 CH3 CH3 H3C H3C O 

O 

H3C CH3 H3C CH3


HO 

HO 

HO 

O 

O 

O 

O 

OH 

OH 

P. Karst. (Hapalopilus P. Karst.) amounting up 

to 43% of its dry weight. Betulinans A (60) and B 

O 

O 

(61) are two simple terphenylquinones recently 

H3CO O 

found in the plant pathogen Lenzites betulina (L.) 

The striking OH O yellowish or orange-coloured fruit- 

OH 

ing HO bodies of the wood-rotting OH edible mushroom 

Laetiporus sulphurous (Bull.) Murrill (Laetiporus 

O O 

Murrill), HO belonging to the Fomitopsidaceae family, 

Fr. (Lenzites Fr.) (Lee et al. 1996; Gill 1999). The 

OCH3 OCH3 labile 2,3,4-trihydroxycinnamyl O 

alcohol is the O building 

block of the purpurogallin (benzotropolone) 

contains non-isoprenoid polyene known as laetiporic 

N 

acid A (predominantly occurring as the 7-cis-isomer, COOH 

HO 

OH 

66) and 2-dehydro-3-deoxylaetiporic acid A (67) 

derivative fomentariol 60. betulinan A(62) produced 61. by betulinan the plant B 

pathogen, the Tinder Fungus, Fomes fomentarius 

as the 62. main fomentariol pigments (Davoli et al. 63. 2005). cinnabarinic acid 

(L.) Fr. of the genus Fomes (Fr.) Fr. (Polyporaceae) 

OCH3 (Steglich & Zechlin 1978). OH 

Pigments with a phenoxazine O 

OH 

chromophore 

HO 

O 

6 Russulales 

O 

widely occur in lichens and to a smaller extent Apart from carotenoids, only a few lower ter- 

H O 

3CO 

in higher fungi of the Polyporaceae family. The R penoids areO coloured compounds. The colour of 

OCH3 cinnabar red pigment HO of the wood-rotting fungus the injured flesh as well as of the latex of several 

HO 

Pycnoporus cinnabarinus (Jacq.) P. Karst. (Pycnopo- Lactarius Pers. (Russulaceae) species own to their 

rus P. Karst.) is 2-amino-3H-phenoxazin-3-one- 

64. corticin A 65. xylerythrin, colour changes R = H to sesquiterpenoids. The young 

1,9-dicarboxylic acid named cinnabaric acid (63). peniophorin, fruiting body R = OH of L. deliciosus (L. ex Fr.) S. F. Gray 

It is biosynthesized from 3-hydroxyanthranilic acid 

units formed as the tryptophan transformation 

is first carrot-coloured, but slowly turns green 

H3C O 

on aging. The young L. deterrimus Gröger fruit- 

products (Gripenberg 1958a). 

The cobalt Crust Fungus Terana caerulea (Lam.) 

ing body CH is pale peach coloured and becomes 

3 

apricot coloured with a greyish green shades on 

Kuntze (Terana Adans.) of the Phanerochaetaceae aging. On cutting, L. deterrimus yields saffron or 

family contains O 

HOOC corticins A (64), B and C as the orange coloured latex. These colour changes are 

colourless quinhydrones OH that are oxidized to the due to sesquiterpenoids CH3 derived from azulene. The 

indigo-blue pigmentOin hymenal surface (Briggs compounds responsible O for these colour changes 

66. laetiporic acid A 

O 

et al. 1976). HOThe 

saprophytic fungus Phanerochaete in L. deliciosus are the blue lactarazulene, i.e. 

O 

O O 

sanguine HO (Fr.) Pouzar (Phanerochaete P. Karst.) con- HO H1,4-dimethyl-7-(1-methylethenyl)azulene (68), and 

3C O 

O 

O 

tains xylerythrin-type pigments (65). Their struc- lipophilic red-violet lactaroviolin, i.e. 4-methyl- 

HO 

HO 

tures suggest a biosynthesis from threeOH molecules of 7-(1-methylethenyl)azulene-1-carbaldehyde CH3 OH 

(68). 

arylpyruvic acids. The wood infected OH by this fungus is However, neither lactarazulene OH nor lactaroviolin 

 

 

then coloured dark red by its mycelium (Gripenberg occurs as such. The orange colour of the fungus 

1965; 58.hypholominB Gripenberg & Martikkala 1970). is due 59.inoscavinA 

to the labile and easily oxidizable dihy- 

H 3CO 

HOOC 

O 

O 

R 

HO 

OH 

HO 

97 

68. lactarazulene, R = CH3 

O 

OH 

lactaroviolin, R = CH=O 

69. dihydroazulen-1-ol (R = H) 70. 1,3,5,7(11),9-pentaenyl-14-guaianal 

HO 

CH 3 

O 

O O 

58. hypholomin B 59. inoscavin A 

OCH 

H3C3 O 

67. 2-dehydro-3-deoxylaetiporic acid HO A 

 

H 3 C 

CH 2 

O 

O 

OCH 

N NH2 3 H3C H3C COOH 

HO 

OH 

 

 

RO 

HO 

60.betulinanA 61.betulinanB 62.fomentariol 63.cinnabarinicacid 

H 3CO 

OCH 3 

O 

OCH 3 

R 

H 3C 

OH 

CH2 O 

O 

O 

O 

OH 

O 

OH 

O 

O 

OH 

O 

OH 

H 3 C 

O 

CH 3 

 

NH 2

O 

OH O 

O 

OH 

H HO 

O 

O 

3CO 

O 

O O 

OH 

O 

H 

HO O 

3CO 

H3CO O 

O R O 

O 

O 

OCH3 HO OCH OCH N NH 

3 

2 

3 

HO 

O 

O 

HO 

COOH 

OCH Vol. 29, 2011, No. 3 2: 87–102 OCH 

CH N NH2 3 

3 

HO 

OH 

 

 


O 

O 

COOH 

O 

64.corticinA HO 

O OH 65.xylerythrin,R=H 

HO 60.betulinanA 

61.betulinanB 

O 62.fomentariol 

63.cinnabarinicacid 

 

peniophorin,R=OH 

O 

O O 

60.betulinanA HO 

61.betulinanB 62.fomentariol HO 

O 63.cinnabarinicacid 

O 

OCH3 O 

H3C O 

OH 

HO 

HO 

OHO 

OCH3 OH 

O OH HO OH 

OH 

CH3 O 

OH OH 

O OH 

 

 

H O 

3CO 

O R 

58.hypholominB 

H O 

59.inoscavinA O 

OCH3 3CO 

HOOC 

HO 

R 

O HO 

OCH OH 

3 

OH O 

 

 

HO 

HO 

OH 

64.corticinA 

O 

HO 

O 

65.xylerythrin,R=H 

OH 

66.laetiporicacidA 

64.corticinA H 

3CO 

 

 

O 

O O 

 

 

65.xylerythrin,R=H 


HO 

H O 


3C H3C O 

OCH3 OCH 

N NH2 3 

O 

H3C O 

CH 

O 

COOH 

3 

HO 

CH OH 

3 

 

 

 

 

60.betulinanA 61.betulinanB 

CH 

62.fomentariol 3 

63.cinnabarinicacid 

HOOC 

droazulen-1-ol HO (69, R=H) or to their stearates, HO uvidin A and B (71) CH3 illustrate the broad variety of 

 

 

69, R = CO[CH ] CH . Recently, three other red compounds found in L. uvidus (Fr.) Fr. Drimane 

2 16 3 CH3 azulene 64.corticinA pigments have been isolated 65.xylerythrin,R=H 

from the sesquiterpenoids like drimenol (72) and uvidins 

fruiting bodies of L. deliciosus being 7-acetyl-4- 

peniophorin,R=OH CH 

have R so far been 2found 

only RO in L. uvidus, CHwhich 2 

methylazulene-1-carbaldehyde, 7-(1,2-dihydroxy- has a white H3Clatex rapidly turning violet H3C H on expo- 

3C O 

 

 

1-methylethyl)-4-methylazulene-1-carbaldehyde sure to the air. 

HOOC 

68.lactarazulene,R=CH3 69.dihydroazulen1ol(R=H) 70. 

and 7-acetyl-4-methylazulene-1-carboxylic acid Intact CH3 fruiting bodies of Lactarius fuliginosus 

lactaroviolin,R=CH=O 

(Xang HOOC et al. 2006; Zhou & Liu 67.2dehydro3deoxylaetiporicacidA 

2010). The red (Krapf 

) Fr. and L. picinus Fr. contain the isoprenoid 

pigment 1,3,5,7(11),9-pentaenyl-14-guaianal (70) quinol stearate of 4-methoxy-2-(3-methylbut-2- 

67.2dehydro3deoxylaetiporicacidA 

was HOOC found in L. sanguifluus H3C H (Paulet) Fr., the lienyl)phenol 3C (73). The pink-red stain and acrid H3C pophilic pigment OH 

H 1-hydroxymethyl-4-methyl- taste that develops when the toadstool is bruised 

3C H3C 

H3C 7-(1-methylethenyl)azulene stearate; 68, R = are due to its hydrolysis followed by oxidation to 


CH OCO[CH ] CH , is responsible CH for the bril- a variety of red benzofurans and chromenes (De 

2 2 16 3 R 

2 

RO 

CH 

CH 

2 

O 

3 

liant blue colour CH of the Indigo Milk H Cap L. indigo H3C O Bernardi et al. 1992). 

2 

3C H3C R 

RO 

CH 

CH H 

2 

3 

3C 

O 

 

 

(Schwein.) Fr. (native to America and Asia and The pale green aminobenzoquinone blennione 

H3C H3C H3C also reported from68.lactarazulene,R=CH3 southern France) (Harmon 69.dihydroazulen1ol(R=H) CH3(74) occurs in the fruit bodies 70.1,3,5,7(11),9pentaenyl14guaianal 

of the common 

et al. 1980; Ayer &lactaroviolin,R=CH=O 68.lactarazulene,R=CH3 Browne 69.dihydroazulen1ol(R=H) 1981; Koul et al. toadstool, 70.1,3,5,7(11),9pentaenyl14guaianal 

the Slimy Milkcap Lactarius blen- 


1985; De Rosa & De Stefano 1987). 

nius (Fr.) Fr. It is probably biosynthesized using 

The milky juice of L. scrobiculatus (Scop.) Fr. 3,6-dihydroxyanthranilic acid units (Spiteller & 

turns rapidly from white to yellow. A range of Steglich 2002). Biosynthetically closely related to 

lactarane HOOC and secolactarane sesquiterpenoids, bennione is the red pigment lilacinone (75), which 

analogues of the above azulenes, have been iso- is responsible for the violet colour of Lactarius 

lated (Bosetti 67.2dehydro3deoxylaetiporicacidA 

et al. 1989). The structures of lilacinus (Lasch) Fr. (Spiteller et al. 2003). 

98 

H 3CO 

R 

OH 

H 3 C 

O 

H 3 C 

OH 

OCH 3 

CH 2 

HOOC 

OCH OH3 

OH 


O 

 

RO 

H 3C 

O 

HO 

HOOC 

66.laetiporicacidA 

O 

R 

H3C H 3C 

CH 2 

O 

O 

H 3 C 

 

67.2dehydro3deoxylaetiporicacidA 

H3C O 

68.lactarazulene,R=CH3 69.dihydroazulen1ol(R=H) 70.1,3,5,7(11),9pentaenyl14guaianal 


O 

 

H 3 C 

H 3 C 

H 3C 

CH 3


OH 

OH 

H 

H 3C 

3C 

CH 

CH 3 

3 

O 

O 

R 

R 

H 

H 

3C CH3 H O 

3C CH3 O 

 

 

OH 

OH 

H 

H 3C 

3C 

CH 

CH 3 

3 

H 

H 

3C CH 

H 3 

3C CH3 

 

 

 

 

OCH 

OCH 3 

3 

OH 

OH 

CH3CH 3 

CH3CH 3 

 

71.uvidinA,R=H 


 

uvidinB,R=OH 

uvidinB,R=OH 

 

72.drimenol 

72.drimenol 

 

 

 

73.4methoxy2(3methylbut2enyl)phenol 

73.4methoxy2(3methylbut2enyl)phenol 

O 

HO 

O 

HO 

OCH3 O 

H2N OH 

N 

OCH OH 

3 O 

H2N OH 

N 

OH OH 

OCH 

OCH 3 OHOCH 

H2N COOH 

3 

3 

OCH3 H2N H3C COOH 

CH H H3C 3 

3C 

HOOC CH CH H 

3 N 

3C 

3 

NH CH 

HOOC N 

2 3 

H 

N 

O 

NH2 HOOC 

NH H O 

N 

2 

O 

HOOC 

NH O 

2 

O 

CH3 CH3 R 

O 

H OH O 

R 

O O COOH 

O OH 

OH O 

H H 

O COOH H 

H 

 

 

CH 

 

O OH 

3C CH3 O 

H3CH 3C CH 3 O 

H CH OH CH 

 

 

3 

3C 

OH CH 

3 

3 

3 

 

 

 

 

74.blennione 

74.blennione 

75.lilacinone 

75.lilacinone 

 

 

 

 

 

 

76.necatarone 

76.necatarone 

71.uvidinA,R=H 71.uvidinA,R=H 72.drimenol 72.drimenol 73.4methoxy2(3methylbut2enyl)phenol 

73.4methoxy2(3methylbut2enyl) 

uvidinB,R=OH 

2 

1 

2 R 

uvidinB,R=OH 

1 R 

R 

R 

OH N 

N 

An alkaloidal pigment necatarone (76), its dehydrodimer 

(77, R1 = R2 = OH) prevailing in aged 

fruiting bodies and the 10-deoxydehydrodimer 

(77, R1 = H, R2 N 

N 

OH 

O 

batrellaceae), which OCHincluded e.g. the purple pig- 

O 3 HO 

H3C OCH CH H 

3 

3C 

ment grifolinone B (80), the red ketone albatrellin 

3 O 

H2N OCHCH 3 O3 

OH 

N 

OCH 

H2N OH 

3 

OCH3 H N O 

(81) and a variety of related compounds of the 

2N COOH 

N 

N 

N H2N COOH 

CH3 R 

H = OH) are the principal HOOC pigments N 

H 

mushroom NH HOOC 2 A. confluens N (Alb. & Schwein.) NH Kotl. 

2 

H CH O OH HO O 

H 

N 

H 

of HOOC the 3C 3 green-brown O 

OHNH HOflesh 

OandH 

HOOC cap 3C CHskin 3 of O Lacta- NH & Pouzar (Yang O 

OH CH 

et al. 2008). 3 

2 

O 

 

2 

O 

O 

 

rius turpis OH (Weinm.) O Fr. (Fugmann 

O COOH 

O 

et OHal. 

O1984, 

The Orange Tooth Hydnellum O Oaurantiacum 

COOHOH 


Klamann 

77.necataronedehydrodimer 

72.drimenol 73.4methoxy2(3methylbut2enyl)phenol 

 

 


et al. 1989). 

(Batsch) P. Karst. (Hydnellum P. Karst., Peniophora- 

uvidinB,R=OH 

74.blennione 74.blennione 75.lilacinone 75.lilacinone 76.necatarone 

 

Ochroleucins are the OCHmain pigments of the fruitceae) colour is derived from the terphenylquinone 

3 

OH 

OCH3 OH 

ing 2bodies 

of the Common Yellow 2Russula, 

1 O Russula atromentin. The 3,6-dibenzoylatromentin, HO 

named 

R 

O R 

1 

CH R 

O 

2 

ochroleuca Pers. and OR. 

viscida OH Kudrna CH O 

OCH3 O 

H 2 (Russula aurantiacin, was first isolated as a dark red pig- 

OH 

2N 

OH 

N 

N 

N 

N 

N OCH3 Pers., H2N Russulaceae). COOHThe 

labile yellow ochroleucin 

CH ment from this mushroom and subsequently from 

H2C H 

CH 3 

H2C CH 

H 2 

A (78) 2C H 

3 

is rapidly transformed OCH HOOC 

H 

3 to the stable N red 2C various Hydnellum O 

CH 

OCH NH species (Gripenberg 2 

2 

1956; 

3 

O 

O 

H 

N 

HOOC N 

ochroleucin CHB 3 (79) O 

N 

N 

(Sontag et al. 2006). Gripenberg CH 1958b). O O 

CH 

CH 

NH N 

O 

2 

O 

3 O Aurantiacin is 3 accompanied 

3 

CH 

O 

CH 

3 

3 

 

O 

 

OH O 

O COOH 

O OH 

Dimeric O meroterpenoid OH HO pigments have been with the corresponding leucoform dihydroauran- 

78.ochroleucinA 

O 

O OH HO O 

79.ochroleucinB 

 

 

reported from 78.ochroleucinA the Albatrellus Gray species (Altiacin and 79.ochroleucinB 

thelephoric acid. 

74.blennione 75.lilacinone 76.necatarone 

HO 

N 

76.nec 

77.necataronedehydrodimer O 

O 


O 

H3C OH 

O 

CH3 O CH3 CH3 CH 

H 3 

3C CH3 OH 

CH3 HO CH3 

80.grifolinoneB 

H3C OH 

O 

CH3 O CH3 CH3 O CH 

H 3 

3C CH3 OH 

CH3 HO CH3 

81.albatrellin 

HO 

H3C O 

H3C CH3 + 

CH3 O OH 

HO 

- 

OH 

N 

O O O 

N 

O 

OH 

N 

O 

N 

HO 

O O 

OH 

HO OH 

 

- H3C OH 

O 

CH3 O CH CH CH 

H 3 

3 

3 

3C CH3 OH 

H3C CH3 HO CH3 

80.grifolinoneB 

O 

H3C OH 

O 

CH3 O CH3 CH3 O CH3 CH3 OH 

CH3 HO CH3 


HO 

H3C O 

H3C CH3 + 

CH3 O OH 

H3C O 

O O 

H3C CH3 H O O 

3C CH3 + 

CH3 OH 

HO 

82.sarcoviolin 

 

83.sarcodonin 

 

- 

O 

OH 

N 

O O 

N 

O 

OH 

N 

O 

N 

HO 

O O 

OH 

HO OH 

 

- 2 

1 

R 

R 

OCH 

N 

3 N 

OCH3 O 

CH2 O 

OH 

OH 

N 

N CH 

H2C H 

3 

H2C H H2C OCH3 OCH3 O OH HO O 

CH 

O 

O 

3 

CH CH 3 

3 

 


78.ochroleucinA 78.ochroleucinA 

OH 

OH 

CH 

O 

O 

2 

CH3 H2C CH2 CH2 O 

O 

O O 

CH CH O O 

CH 

3 

3 

3 

 

 

 

79.ochroleucinB 79.ochroleucinB 

OCH3 O 

O 

OH O 

O 

H2C H3C CH3 CH3 H3C O 

H 

OCH3 O 

OH 

H3C OH 

O 

CH2 OH 

O CH3 CH3 H2C O CH3 CH3 CH3O CH H3C 3 OH 

CH H 

3 3C CH CH 

3 

3 

H3C OH 

O 

H3C H3C OH 

O 

O O 

H 

CH 3C 

O 

CH 

3 

O 3 CH3 H O O 

3C CH CH 3 

2 + 

CH3 O CH3 O CH CH 3 3 CH3 O CH CH3 3O 

OH 

H3C CH 

O O 

CH3 OH 

CH OH 

3 

CH 3 

3 

CH 

 

3 

CH3 OH 

78.ochroleucinA 

HO 

82.sarcoviolin 

O 

H3C 80.grifolinoneB OH 

CH3 79.ochroleucinB 

HO CH3 HO CH3 

83.sarcodonin 

O 

80.grifolinoneB H3C 81.albatrellin 

OH 

HO 

 


CH 

 

H 3 C 

HO 

 

CH 3 

O 

H3C O 

H3C 99 

CH3 + 

CH3 HO 

O OH 

- 

OH 

N 

O O O 

O 

N 

N 

O 

HO 

O O - 

H3C CH3 O 

CH 

O 

3 H3C O 

O O 

H 

O 

3C 

CH CH CH CH 

H3C 3 

3 3 

3 

O CH3 CH3 O CH3 CH3 OH 

H3C CH 

+ 

3 OH 

H O O 

3C CH 

CH 3 + 

CH3 3 

O OH 

- 

OH 

OH 

N 

N 

O O O 

O 

N 

N 

O 

HO 

O O - H3C O 

O O 

H3C CH3 H O O 

3C CH3 + 

CH3 OH 

HO 

OH 

HO CH 3 

 

HO CH 3

H 3 C 

100 

CH 3 

O 

CH 3 

CH3 OH 

7 Thelephorales 

 

The fruiting bodies of Sarcodon leucopus (Pers.) 

Maas Geest. & Nannf. (Sarcodon Quél. ex P. Karst., 

Bankeraceae) contain a range of compounds related 

to terphenylquinones. The main pigments are the 

unusual nitrogenous violet terphenylquinols sarcoviolins, 

exemplified by sarcoviolon α (82), which 

are accompanied by their colourless precursors 

sarcodonins (83) and structurally related compounds 

(Geraci et al. 2000; Cali et al. 2004). 

R e f e r e n c e s 

CH 3 

CH 3 

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HO 

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82.sarcoviolin 83.sarcodonin 

 

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Recieved for publication December 29, 2010 

Accepted after corrections January 15, 2011 

Corresponding author: 

Prof. Ing. Jan Velíšek, DrSc., Vysoká škola chemicko-technologická v Praze, Fakulta potravinářské a biochemické 

technologie, Ústav chemie a analýzy potravin, Technická 5, 166 28 Praha 6, Česká republika 

tel.: + 420 220 443 175, e-mail: jan.velisek@vscht.cz

Pigments of Higher Fungi: A Review

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