In this review the biogenesis, structures, and bioactivities of all sesquiterpenoids isolated from Russula and Lactarius species in the last decade are critically discussed, and divided into sections according to their skeletons. A brief chemotaxonomic overview of the family Russulaceae is reported in the final part of the review.
This paper is Part 54 of the series “Fungal Metabolites”. Part 53: ClericuzioM, TabassoS, GarbarinoJA, PiovanoM, CardileV, RussoA, VidariG. (2007) Non-phenolic dicinnamamides from Pholiota spumosa: Isolation, synthesis and antitumor activity. European Journal of Organic Chemistry, 5551–5559.
2.
SingerR. (1986) The Agaricales in Modern Taxonomy. Koeltz Scientific, Koenigstein.
3.
BonM. (1980) Clé Monographique du Genre Lactarius (Pers. Ex Fr.) GrayS. F.Documents Mycologiques, 10, 1–85.
SarnariM. (1998) Monografia illustrata del genere Russula in Europa, Vol. 1. Associazione Micologica Bresadola, Trento.
6.
SarnariM. (2004) Monografia illustrata del genere Russula in Europa, Vol. 2. Associazione Micologica Bresadola, Trento.
7.
VidariG, Vita FinziP. (1995) Sesquiterpenes and other secondary metabolites of genus Lactarius (Basidiomycetes): Chemistry and biological activity. In Studies in Natural Products Chemistry. Structure and Chemistry (Part D). Vol. 17, Atta-ur-Rahman (Ed). Elsevier, London, UK, 153–206;
8.
DaniewskiWM, VidariG. (1999) Constituents of Lactarius (mushrooms). In Fortschritte der Chemie organischer Naturstoffe. Vol 77, HerzW, FalkH, KirbyGW, MooreRE, TammCh (Eds). Springer, New York, 69–171.
9.
RomagnesiH. (1985) Les Russules d'Europe et d'Afrique du Nord.J. Cramer, Vaduz.
10.
SternerO, BergmanR, KihlbergJ, WickbergB. (1985) The sesquiterpenes of Lactarius vellereus and their role in a proposed chemical defence system. Journal of Natural Products, 48, 279–288;
11.
SternerO, BergmanRFranzénC, WickbergB. (1985) New sesquiterpenes in a proposed Russulaceae chemical defense system. Tetrahedron Letters, 26, 3163–3166.
12.
Favre-BonvinJ, Gluchoff_FiassonK, BernillonI. (1982) Structure du stearyl-velutinal, sesquiterpenoids naturel de Lactarius velutinus Bert. Tetrahedron Letters, 23, 1907–1908;
13.
Gluchoff-FiassonK, KühnerR. (1982) Le principe responsable du bleuissement au réactif sulfovanillique des cystides et lacticifères de divers Homobasidiomycètes: intérèt systématique. Comptes Rendus de l'Academie des Sciences Series III, 294, 1067–1071.
14.
AnkeH, SternerO. (1991) Comparison of the antimicrobial and cytotoxic activities of twenty unsaturated sesquiterpene dialdehydes from plants and mushrooms. Planta Medica, 57, 344–346.
15.
De BernardiM, VidariG, Vita FinziP. (1982) Biogenesis-like conversion of marasmane to lactarane and seco-lactarane skeleton. Tetrahedron Letters, 23, 4623–4624.
16.
SternerO, BergmanR, KihlbergJ, OluwadiyaJ, WickbergB, VidariG, De BernardiM, De MarchiF, FronzaG, Vita FinziP. (1985) Basidiomycete sesquiterpenes: The silica gel induced degradation of velutinal derivatives. Journal of Organic Chemistry, 50, 950–953.
17.
AyerWA, NakashimaTT, Saeedi-GhomiMH. (1984) Studies on the biosynthesis of the sterpurenes. Canadian Journal of Chemistry, 62, 531–533.
18.
LinH; LiuJK. (2002) The first humulene type of sesquiterpene from Lactarius hirtipes. Zeitschrift fuer Naturforschung, C: Journal of Biosciences, 57, 571–574.
19.
LouDQ, GaoY, GaoJM, YangX, LiuJK. (2006) Humulane type of sesquiterpenoids from the mushroom Lactarius mitissimus. Journal of Natural Products, 69, 1354–1357.
20.
LouDQ, GaoY, YangXL, TangJG, LiuJK. (2007) Highly Oxidized Humulane Sesquiterpenes from the Basidiomycete Lactarius mitissimus. Journal of Antibiotics, 60, 162–165.
21.
LouDQ, GaoY, YangXL, TangJG, ZhaoLY, LiuJK. (2007) Two new highly oxidized humulane sesquiterpenes from the basidiomycete Lactarius mitissimus. Helvetica Chimica Acta, 90, 1112–1116.
22.
DaniewskiWM, GriecoPA, HoffmanJC, RymkiewiczA, WawrzunA. (1981) 12-Hydroxycaryophyllene-4,5-oxide, a sesquiterpene from Lactarius camphorates. Phytochemistry, 20, 2733–2734.
23.
ClericuzioM, TomaL, VidariG. (1999) Fungal metabolites 44. Isolation of a new caryophyllane ester from Lactarius subumbonatus: Conformational analysis and absolute configuration. European Journal of Organic Chemistry, 2059–2065.
24.
De VoeH. (1965) Optical properties of molecular aggregates II. Classical theory of the refraction, absorption and optical activity of solutions and crystals. Journal of Chemical Physics, 43, 3199–3208.
25.
KusumiT, TakahashiH, XuP, FukushimaT, AsakawaY, HashimotoT, KanY, InouyeY. (1994) New chiral anisotropic reagents, NMR tools to elucidate the absolute configurations of long-chain organic compounds. Tetrahedron Letters, 35, 4397–4400;
26.
SecoJM, LatypovS, QuinoaE, RigueraR. (1994) New chirality recognizing reagents for the determination of absolute stereochemistry and enantiomeric purity by NMR. Tetrahedron Letters, 35, 2921–2924.
27.
YangXL, LuoDQ, LiuJK. (2006) A new pigment from the fruiting bodies of the Basidiomycete Lactarius deliciosus. Zeitschrift fuer Naturforschung, C: Journal of Biosciences, 61, 1180–1182.
28.
YangXL., LuoDQ., LiuJK. (2006) Two new pigments from the fruiting bodies of the Basidiomycete Lactarius deliciosus. Helvetica Chimica Acta, 89, 988–990.
29.
BergendorffO, SternerO. (1988) The sesquiterpenes of Lactarius deliciosus and Lactarius deterrimus. Phytochemistry, 27, 97–100
30.
FangLZ, ShaoHJ, YangWQ, LiuJK. (2006) Two new azulene pigments from the fruiting bodies of the Basidiomycete Lactarius hatsudake. Helvetica Chimica Acta, 89, 1463–1466.
31.
YoshikawaK, ToriK, AriharaS, SasakiT. (2001) A new eudesmane sesquiterpene from the fruit body of Lactarius laeticolorus. Natural Medicines, 55, 87–89.
32.
VidariG, CheZ, GarlaschelliL. (1998) New nardosinane and aristolane sesquiterpenes from the fruiting bodies of Russula lepida. Tetrahedron Letters, 39, 6073–6076.
33.
TanJW, DongZJ, LiuJK. (2000) New terpenoids from Basidiomycetes Russula lepida. Helvetica Chimica Acta, 83, 3191–3197;
34.
TanJ, DongZ, LiuJ. (2001) New sesquiterpenoid from Russula lepida Zhiwu Xuebao, 43, 329–330. CAN 135:315641.
35.
TanJ, DongZ, LiuJ. (2003) Lepidamine, the first aristolane-type sesquiterpene alkaloid from the Basidiomycete Russula lepida. Helvetica Chimica Acta, 86, 307–309.
36.
VidariG, GarlaschelliL, RossiA, Vita FinziP. (1998) New protoilludane sesquiterpenes from Lactarius violascens. Tetrahedron Letters, 39, 1957–1960.
37.
ClericuzioM, MellaM, TomaL, Vita FinziP, VidariG. (2002) Atlanticones, new protoilludane sesquiterpenes from the mushroom Lactarius atlanticus (Basidiomycetes). European Journal of Organic Chemistry, 988–994.
38.
CamazineS, LupoATJ. (1984) Labile toxic compounds of the Lactarii: the role of the lacticiferous hyphae as a storage depot for precursors of pungent dialdehydes. Mycologia, 76, 355–358.
39.
WangY, YangSP, YueJM, ChowS, KitchingW. (2003) Novel sesquiterpenes from the fungus Lactarius piperatus. Helvetica Chimica Acta, 86, 2424–2433.
40.
ClericuzioM, FuJ, PanF, PangZ, SternerO. (1997) Structure and absolute configuration of protoilludane sesquiterpenes from Russula delica. Tetrahedron, 28, 9735–9740.
41.
According to our convention [5], the geminal groups at C(11) of protoilludanes and derivatives, are numbered 14 and 15, respectively, depending upon them being trans or cis to the protons 2-H and 9-H. Other authors prefer the opposite convention.
42.
HirotaM, ShimizuY, KamoT, MakabeH, ShibataH. (2003) New plant growth promoters, Repraesentins A, B and C, from Lactarius repraesentaneus. Bioscience, Biotechnology, and Biochemistry, 67, 1597–1600.
43.
KashiwabaraM, KamoT, MakabeH, ShibataH, HirotaM. (2006) Repraesentins D, E, and F, new plant growth promoters from Lactarius repraesentaneus. Bioscience, Biotechnology, and Biochemistry, 70, 1502–1505.
44.
NozoeS, KobayashiH, UranoS, FurukawaJ. (1977) Isolation of Δ6-protoilludene and the related alcohols. Tetrahedron Letters, 1381–1384;
45.
MorisakiN, FurukawaJ, KobayashiH, IwasakiS, NozoeS, OkudaS. (1985) Conversion of 6-protoilludene into illudin M and -S by Omphalotus olearius. Tetrahedron Letters, 26, 4755–4758.
46.
HanssenHP, AbrahamWR. (1988) Sesquiterpene alcohols with novel skeletons from the fungus Ceratocystis piceae (Ascomycotina). Tetrahedron, 44, 2175–2180.
47.
ClericuzioM, PanF, HanF, PangZ, SternerO. (1997) Stearoyldelicone, an unstable protoilludane sesquiterpenoid from intact fruit bodies of Russula delica. Tetrahedron Letters, 38, 8237–8240.
48.
ClericuzioM, HanF, PanF, PangZ, SternerO. (1998) The sesquiterpenoid contents of fruit bodies of Russula delica. Acta Chemica Scandinavica, 52, 1333–1337.
49.
The mushroom was erroneously classified as Russula delica in the original papers [39–41]. Clericuzio M, personal communication.
50.
StranskyK, SemerdzievaM, OtmarM, ProchazkaZ, BudesinskyM, UbikK, KohoutovaJ, StreinzL. (1992) Antifungal antibiotic from the mushroom Agrocybe aegerita (Brig.) Sing. Collection of Czechoslovak Chemical Communications, 590–603.
51.
YoshikawaK, KanekoA, MatsumotoY, HamaH, AriharaS. (2006) Russujaponols A-F, illudoid sesquiterpenes from the fruiting body of Russula japonica. Journal of Natural. Products, 69, 1267–1270.
52.
AndinaD, De BernardiM, Del VecchioA, FronzaG, MellerioG, VidariG, Vita FinziP. (1980) Sesquiterpenes from Russula sardonia. Phytochemistry, 19, 93–97.
53.
ClericuzioM, VidariG, Vita FinziP. Unpublished results.
54.
ClericuzioM, SternerO. (1997) Conversion of velutinal esters in the fruit bodies of Russula cuprea. Phytochemistry, 45, 1569–1572.
55.
YaoitaY, MachidaK, KikuchiM. (1999) Structures of new marasmane sesquiterpenoids from Lactarius piperatus (Scop.: Fr.) S. F. Gray. Chemical and Pharmaceutical Bulletin, 47, 894–896.
56.
VidariG, De BernardiM, Vita FinziP, FronzaG. (1976) Sesquiterpenes from Lactarius blennius. Phytochemistry, 15, 1953–1955.
57.
ShaoHJ, WangCJ, DaiY, WangF, YangWQ, LiuJK. (2007) Pubescenone, a new marasmane sesquiterpenoid from the mushroom Lactarius pubescens. Heterocycles, 71, 1135–1139.
58.
WangXN, WangF, DuJC, GeHM, TanRX, LiuJK. (2005) A new marasmane sesquiterpene from the Basidiomycete Russula foetens. Zeitschrift für Naturforschung, 60b, 1065–1067;
59.
WangXN, ShenJH, DuJC, LiuJK. (2006) Marasmane sesquiterpenes isolated from Russula foetens. Journal of Antibiotics, 59, 669–672.
60.
LuoDQ, WangF, BianXY, LiuJK. (2005) Rufuslactone, a new antifungal sesquiterpene from the fruiting bodies of the Basidiomycete Lactarius rufus. Journal of Antibiotics, 58, 456–459.
61.
GaoJM. (2006) New biologically active metabolites from Chinese higher fungi. Current Organic Chemistry, 10, 849–871
62.
KamoT, MatsueM, KashiwabaraM, HirotaM. (2006) 1,2-Dehydrolactarolide A, a growth regulatory lactarane sesquiterpene from Lactarius vellereus. Bioscience, Biotechnology, and Biochemistry, 70, 2307–2309.
63.
SuriOP, ShahR, SattiNK, SuriKA. (1997) Russulactarorufin, a lactarane skeleton sesquiterpene from Russula brevipes. Phytochemistry, 45, 1453–1455.
64.
KobataK, KanoS, ShibataH. (1995) New lactarane sesquiterpenoid from the fungus Russula emetica. Bioscience, Biotechnology, and Biochemistry, 59, 316–318.
65.
De BernardiM, FronzaG, MellerioG, VidariG, Vita FinziP. (1979) New sesquiterpene hydroxylactones from Lactarius species. Phytochemistry, 18, 293–298.
66.
YaoitaY, OtoH, KikuchiM. (2003) A new norsesquiterpenoid from Russula delica Fr. Chemical and Pharmaceutical Bulletin, 51, 1003–1005.
67.
KopczackiP, GumulkaM, MasnykM, GrabarczykH, NowakG, DaniewskiWM. (2001) Synthesis and antifeedant properties of N-benzoylphenylisoserinates of Lactarius sesquiterpenoid alcohols. Phytochemistry, 58, 775–787;
68.
DaniewskiWM, GumulkaM, KopczackiP, MasnykM. (2001) Synthesis of N-enzoylphenylisoserinates of lactarorufin B (a sesquiterpene of Lactarius origin) and its derivatives. Polish Journal of Chemistry, 75, 1287–1296;
69.
SarosiekA, MasnykM, GumulkaM, DaniewskiWM, KobusM, KrawczykE, LuczakM. (2002) Synthesis and cytotoxic properties of N-boc-phenylisoserinates of sesquiterpenoic alcohols from mushrooms of Lactarius genus, as analogues of Taxotere. Polish Journal of Chemistry, 76, 73–82;
70.
BaryckiR, GumulkaM, MasnykM, DaniewskiWM, KobusM, LuczakM. (2002) Synthesis of N-acetyl-3-phenylisoserinates of sesquiterpenoid alcohols of Lactarius origin. Collection of Czechoslovak Chemical Communications, 67, 75–82;
71.
KrawczykE, LuczakM, KobusM, BankaD, DaniewskiW. (2003) Antiviral activity of N-benzoylphenylisoserinates of Lactarius sesquiterpenoid alcohols in vitro. Planta Medica, 69, 552–554;
72.
KopczackiP, GumulkaM, MasnykM, SarosiekA, BaryckiR, IgnacakW, ZochowskiS, GrabarczykH, NowakG, DaniewskiWM. (2004) Synthesis and antifeedant properties of N-acylphenylisoserinates of Lactarius sesquiterpenoid alcohols. Polish Journal of Chemistry, 78, 89–108;
73.
SarosiekA, MasnykM, GumulkaM, DaniewskiWM, KobusM, KrawczykE, LuczakM. (2002) Synthesis and cytotoxic properties of N-boc-phenylisoserinates of sesquiterpenoic alcohols from mushrooms of Lactarius genus, as analogues of Taxotere. Polish Journal of Chemistry, 76, 73–82.
74.
BuyckB, MitchellD. (2003) Russula lentiginosa sp. nova from West Virginia, USA: a probable link between tropical and temperate Russula-groups. Cryptogamie-Mycologie, 24, 317–325.
75.
EugsterCH, ItenPX. (1975) Russupteridines. Chemistry and Biology of Pteridines, Proceedings International Symposium, 5th, 881–917. De Gruyter, Berlin-New York.
76.
LarssonE, LarssonKH. (2003) Phylogenetic relationships of russuloid Basidiomycetes with emphasis on aphyllophoralean taxa. Mycologia, 95, 1037–1065.
