Biotransformation of sesquiterpenoids isolated from several liverworts using various fungi and mammals is summarized. Microorganisms introduce an oxygen atom at an allylic position to give secondary hydroxyl and keto groups. The cyclopentane ring is also oxidized to afford monoketo, and mono- and diols. Double bonds are also either reduced or oxidized to give either saturated compounds or epoxides, followed by hydrolysis to afford diols. The methyl group is oxidized to give a primary alcohol. Some fungi cleave the cyclopropane ring to form a 1,1-dimethyl group. These reactions precede stereo- and regio-specifically. Cytochrome P-450 is responsible for the introduction of an oxygen function into the substrates. The present methods are cheap, one step reactions, non-hazardous, and very useful for the production of some bioactive compounds from a large number of terpenoids found in liverworts and higher plants.
AsakawaY. (1982) Chemical constituents of the Hepaticae. In Progress in the Chemistry of Organic Natural Products. HerzW, GrisebachH, KirbyGW (Eds). Springer, Vienna, Austria, 42, 1–285.
2.
AsakawaY. (1995) Chemical constituents of the bryophytes. In Progress in the Chemistry of Organic Natural Products. HerzW, KirbyGW, MooreRE, SteglichW, TammCh (Eds). Springer, Vienna, Austria, 65, 1–618.
3.
AsakawaY. (1990) Terpenoids and aromatic compounds with pharmaceutical activity from bryophytes. In Bryophytes: Their Chemistry and Chemical Taxonomy, ZinsmeisterDH, MuesR (Eds). Clarendon Press, Oxford, UK, 369–410.
4.
AsakawaY. (1999) Phytochemistry of bryophytes. In Phytochemicals in Human Health Protection, Nutrition, and Plant Defense. RomeoJ (Ed). Kluwer Academic, Plenum Publishers, New York, 33, 319–342.
5.
AsakawaY. (2007) Biologically active compounds from bryophytes. Pure and Applied Chemistry, 75, 557–580.
6.
AsakawaY. (2008) Recent advances of biologically active substances from the Marchantiophyta. Natural Product Communications, 3, 77–92.
7.
AsakawaY, LudwiczukA. (2008) Bryophytes-chemical diversity, bioactivity and chemosystematics. Part 1. Chemical diversity and bioactivity. Medicinal Plants in Poland and in the World, 14, 33–53.
8.
HayashiK, MorikawaH, MatsuoA, TakaokaD, NozakiH. (1999) Biotransformation of sesquiterpenoids by Aspergillus niger IFO 4407. Proceedings of the 43rd Symposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Oita, Japan, 208–210.
9.
NozakiH, AsanoK, HayashiK, TanakaM, MasuoA, TakaokaD. (1996) Biotransformation of shiromodiol diacetate and myli-4(15)-en-9-one by Aspergillus niger IFO 4407. Proceedings of the 40th Symposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Saga, Japan, 108–110.
10.
FurusawaM, HashimotoT, NomaY, AsakawaY. (2006) Biotransformation of aristolene- and 2,3-secoaromadendrane-type sesquiterpenoids having a 1,1-dimethylcyclopropane ring by Chlorella fusca var. vacuolata, Mucor species, and Aspergillus niger. Chemical and Pharmaceutical Bulletin, 54, 861–868.
11.
HashimotoT, NomaY, GotoY., TakaokaS, TanakaM, AsakawaY. (2003) Biotransformation of sesquiterpenoids from the liverwort Plagiochila species. Proceedings of the 47th Symposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Tokyo, Japan, 139–141.
12.
MorikawaH, HayashiK, WakamatsuK, TakaokaD, HaraguchiH, MatsuoA, NozakiH. (2000) Biotransformation of sesquiterpenoids by Aspergillus niger IFO 4404. Proceedings of the 44th Symposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Sapporo, Japan, 151–13.
13.
IshidaT, AsakawaY, TakemotoT, ArataniT. (1981) Terpenoid biotransformation in mammals. III. Biotransformation of α-pinene, β-pinene, pinane, 3-carene, carane, myrcene and p-cymene in rabbits. Journal of Pharmaceutical Sciences, 70, 406–415.
14.
IshidaT. (2005) Biotransformation of terpenoids by mammals, microorganisms, and plant-cultured cells. Chemistry and. Biodiversity, 2, 569–590.
15.
NomaY, HashimotoT, KikkawaA, AsakawaY. (1996) Biotransformation of (-)-α-eudesmol by Aspergillus niger and A. cellulosae M-77. Proceedings of the 40thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Saga, Japan, 95–97.
NomaY, HashimotoT, KatoS, AsakawaY. (1997) Biotransformation of (+)-β-eudesmol by Aspergillus niger. Proceedings of the 41stSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Iwate, Japan, 224–226.
18.
HashimotoT, NomaY, MatsumotoY, AkamatsuY, TanakaM, AsakawaY. (1999) Biotransformation of sesquiterpenoids by microorganisms. (6): Biotransformation of α-, β- and γ-cyclocostunolides. Proceedings of the 43rdSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Oita, Japan, 205–207.
19.
HashimotoT, NomaY, AsakawaY. (2001) Biotransformation of terpenoids from the crude drugs and animal origin by microorganisms. Heterocycles, 54, 529–559.
20.
HashimotoT, SekitaM, FurusawaM, NomaY, AsakawaY. (2005) Biotransformation of sesquiterpene lactones, (-)-parthenolide and (-)-frullanolide by microorganisms. Proceedings of the 49thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Fukui, Japan, 387–389.
21.
ClarkAM, HuffordCD. (1979) Microbial transformation of the sesquiterpene lactone costunolide. Journal of the Chemical Society, Perkin Transactions1, 3022–3028.
22.
BarreroAF, OltraJ E, RaslanDS, SadeDA. (1999) Microbial transformation of sesquiterpene lactones by the fungi Cunninghamella echinulata and Rhizopus oryzae. Journal of Natural Products, 62, 726–729.
23.
KumariGNK, MasilamaniS, GaneshR, AravindS. (2003) Microbial biotransformation of zaluzanin D. Phytochemistry, 62, 1101–1104.
24.
ArandaG, FaconI, LallemandJ-Y, LeclaireM. (1992) Microbiological hydroxylation in the drimane series. Tetrahedron Letters, 33, 7845–7848.
25.
SekitaM, FurusawaM, HashimotoT, NomaY, AsakawaY. (2005) Biotransformation of pungent tasting polygodial from Polygonum hydropiper and related compounds by microorganisms. Proceedings of the 49thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Fukui, Japan, 380–381.
26.
AyerWA, CrawPA. (1989) Metabolites of fairy ring fungus, Marasmius oreades. Part 2. Norsesquiterpenes, further sesquiterpenes and argocybin. Canadian Journal of Chemistry, 67, 1371–1380.
27.
SekitaM, HashimotoT, NomaY, AsakawaY. (2006) Biotransformation of biologically active terpenoids, sacculatal and cinnamodial by microorganisms. Proceedings of the 50thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Yokohama, Japan, 406–408.
28.
HashimotoT, NomaY, AsakawaY. (2006) Biotransformation of cuparane- and herbertane-type sesquiterpenoids. Proceedings of The 50thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Yokohama, Japan, 263–265.
29.
FurusawaM, NomaY, HashimotoT, AsakawaY. (2003) Biotransformation of Citrus oil nootkatone, dihydronootkatone and dehydronootkatone, Proceedings of the 47thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Tokyo, Japan, 142–144.
30.
HarinantenainaL, QuangDN, NishizawaT, HashimotoT, KochiC, SomaG-I, AsakawaY. (2007) Bioactive compounds from liverworts: Inhibition of lipopolysaccharide-induced inducible NOS mRNA in RAW 264.7 cells by herbertenoids and cuparenoids. Phytomedicine, 14, 486–491.
31.
HarinantenainaL, NomaY, AsakawaY. (2005) Penicillium sclerotiorum catalyzes the conversion of herbertenediol into its dimers: mastigophorenes A and B. Chemical and Pharmaceutical Bulletin, 53, 256–257.
32.
HashimotoT, NomaY, GotoY, TanakaM, TakaokaS, AsakawaY. (2004) Biotransformation of (-)-maalioxide by Aspergillus niger and Aspergillus cellulosae. Heterocycles, 62, 655–666.
33.
WangY, TanT -K, TanGK, ConnollyJD, HarrisonLJ. (2006) Microbial transformation of the sesquiterpenoid (-)-maalioxide by Mucor plumbeus. Phytochemistry, 67, 58–61.
34.
ToriM, SonoM, AsakawaY. (1990) The reaction of three sesquiterpene ethers with m-chloroperbenzoic acid. Bulletin of Chemical Society of Japan, 63, 1770–1776.
35.
FurusawaM, HashimotoT, NomaY, AsakawaY. (2005) The structure of new sesquiterpenoids from the liverwort Reboulia hemisphaerica and their biotransformation. Proceedings of the 49thSymposium on the Chemistry of Terpenes, Essential Oils, and Aromatics, Fukui, Japan, 235–237.
36.
FurusawaM, HashimotoT, NomaY, AsakawaY. (2006) Isolation and structures of new cyclomyltaylane and ent-chamigrane-type sesquiterpenoids from the liverwort Reboulia hemisphaerica. Chemical and Pharmaceutical Bulletin, 54, 996–1003.
37.
LahlouEL, NomaY, HashimotoT, AsakawaY. (2000) Microbiotransformation of dehydropinguisenol by Aspergillus sp. Phytochemistry, 54, 455–460.
38.
LamareV, FurstossR. (1990) Bioconversion of sesquiterpenes. Tetrahedron, 46, 4109–4132.
39.
DeviJR. (1979) Microbiological transformation of terpenes: Part XXVI. Microbial transformation of caryophyllene. Indian Journal of Biochemistry and Biophysics, 16, 76–79.
40.
AbrahamWR, ErnstL, StumpfB. (1990) Biotransformation of caryophyllene by Diplodia gossypina. Phytochemistry, 29, 115–120.
41.
ChoudharyMI, SiddiquiZA, NawazSA, Atta-ur-Rahman. (2006) Microbial transformation and butyrylcholinesterase inhibitory activity of (-)-caryophyllene oxide and its derivatives. Journal Natural Products, 69, 1429–1434.
42.
DuranR, CorralesE, Hernandez-GalanR, ColladoG. (1999) Biotransformation of caryophyllene oxide by Botrytis cinerea. Journal of Natural Products, 62, 41–44.
43.
AsakawaY, TairaZ, TakemotoT, IshidaT, KidoM, IchikawaY. (1981) X-ray crystal structure analysis of 14-hydroxycaryophyllene oxide, a new metabolite of (-)-caryophyllene in rabbits. Journal of Pharmaceutical Sciences, 70, 710–711.
44.
DaniewskiWM, GriecoPA, HuffmanJ, RymkiewiczA, WawrzunA. (1981) Isolation of 12-hydroxycaryophyllene-4,5-oxide, a sesquiterpene from Lactarius camphorates. Phytochemistry, 20, 2733–2734.
45.
AsakawaY, IshidaT, ToyotaM, TakemotoT. (1986) Terpenoid biotransformation in mammals IV. Biotransformation of (+)-longifolene, (-)-caryophyllene, (-)-caryophyllene oxide, (-)-cyclocolorenone, (+)-nootkatone, (-)-elemol, (-)-abietic acid and (+)-dehydroabietic acid in rabbits. Xenobiotica, 6, 753–767.
46.
AsakawaY. (unpublished results).
47.
FurusawaM, HashimotoT, NomaY, AsakawaY. (2005) Highly efficient production of nootkatone, the grapefruit aroma from valencene, by biotransformation. Chemical and Pharmaceutical Bulletin, 53, 1513–1514.
48.
FurusawaM, HashimotoT, NomaY, AsakawaY. (2005) Biotransformation of Citrus aromatics nootkatone and valencene by microorganisms. Chemical and Pharmaceutical Bulletin, 53, 1423–1429.
