Biotransformations of Acyclic Terpenoids
J. Agric. Food Chem., Vol. 44, No. 6, 1996 1547
Abraham, W.-R.; Hoffmann, H. M. R.; Kieslich, K.; Reng, G.;
Stumpf, B. Microbial transformations of some monoterpe-
noids and sesquiterpenoids. Ciba Found. Symp. 1985, 111
(Enzymes Org. Synth.), 146-150.
Abraham, W.-R.; Stumpf, B.; Alfmann, H.-A. Chiral intermedi-
ates by microbial epoxidations. J . Essent. Oil Res. 1990, 2,
251-257.
Alfmann, H.-A.; Abraham, W.-R.; Kieslich, K. Microbial ω-hy-
droxylations of trans-nerolidol and structurally related
sesquiterpenoids. Biocatalysis 1988, 2, 59-67.
Hashidoko, Y.; Urashima, M.; Yoshida, T.; Mizutani, J . De-
carboxylative conversion of hydroxycinnamic acids by Kleb-
siella oxytoca and Erwinia uredovora, epiphytic bacteria of
Polymnia sonchifolia leaf, possibly associated with formation
of microflora on the damaged leaves. Biosci., Biotechnol.
Biochem. 1993, 57 (2), 215-219.
al., 1989; Abraham and Stumpf, 1987; Madyastha and
Gurura, 1993; J uttner and Hans, 1986) indicates that
5 is (E)-9,10-dihydroxy-6,10-dimethyl-5-undecen-2-one.
Metabolite 6 has a molecular formula of C13H24
O
based on its mass spectrum. Its spectral data indicated
the presence of a secondary hydroxyl group (δH 3.81; δC
67.91), two trisubstituted double bonds [δH 5.14, δC
123.94 (CH) and 135.65 (C); and δH 5.08; δC 124.25 (CH)
and 131.38 (C)], and no carbonyl group. From the
spectral data, metabolite 6 is elucidated to be (E)-6,10-
dimethyl-5,9-undecadien-2-ol.
Metabolite 7 has a molecular formula of C13H24O2
based on its mass spectrum. Its spectral data indicated
the presence of a tertiary hydroxyl group (δC 70.69; νmax
3425, 1158 cm-1), a trisubstituted double bond [δH 5.08;
δC 122.56 (CH) and 136.16 (C)] bearing a methyl group
(δH 1.61; δC 15.71), and a carbonyl group (δC 208.76; νmax
1713 cm-1). From the spectral data, metabolite 7 is
elucidated to be (E)-10-hydroxy-6,10-dimethyl-5-unde-
cen-2-one.
Holmes, D. S.; Asworth, D. M.; Robinson, J . A. The biocon-
version of (3RS,E)- and (3RS, Z)-nerolidol into oxygenated
products by Streptomyces cinnamonensis. Possible implica-
tions for the biosynthesis of the polyether antibiotic mon-
ensin A? Helv. Chem. Acta 1990, 73, 260-271.
J uttner, F.; Hans, R. The reducing capacities of cyanobacteria
for aldehydes and ketones. Appl. Microbiol. Biotechnol.
1986, 25, 52-54.
Kieslich, K.; Hoyer, G.-A.; Seeger, A.; Wiechert, R.; Kerb, U.
Preparation of several mono- and diketo-structures of
D-homo-4-pregnene-3,20-dione and D-homo-1,4-pregnadiene-
3,20-dione. Chem. Ber. 1980, 113, 203-220.
Kuhn, P. J .; Smith, D. A.; Ewing, D. F. 5,7,2′,4′-Tetrahydroxy-
8-(3′′-hydroxy-3′′-methylbutyl)isoflavanone, a metabolite of
kievitone produced by Fusarium solani f.sp. phaseoli. Phy-
tochemistry 1977, 16, 296-297.
Madyastha, K. M.; Gurura, T. L. Transformations of acyclic
isoprenoids by Aspergillus niger: selective oxidation of
ω-methyl and remote double bonds. Appl. Microbiol. Bio-
technol. 1993, 38, 738-741.
Metabolite 8 has a molecular formula of C13H26O3
based on its mass spectrum. Its spectral data indicated
the presence of two secondary hydroxyl groups (δH 3.33,
δC 73.01; and δH 3.80, δC 67.81), a tertiary hydroxyl
group (δC 77.98; νmax 3382, 1131 cm-1), a trisubstituted
double bond [δH 5.22; δC 124.68 (CH) and 135.27 (C)]
bearing a methyl group (δH 1.63; δC 15.84), and no
carbonyl group. Comparison of spectral data between
8 and 4-7 indicates that 8 is elucidated to be (E)-6,10-
dimethyl-5-undecene-2,9,10-triol.
Metabolite 9 has a molecular formula of C13H26O2
based on its mass spectrum. Its spectral data indicated
the presence of a secondary hydroxyl group (δH 3.80, δC
67.68), a tertiary hydroxyl group (δC 70.85; νmax 3356,
1131 cm-1), and no carbonyl group. Comparison of
spectral data between 9 and 4-8 indicates that 9 is (E)-
6,10-dimethyl-5-undecene-2,10-diol.
Miyazawa, M.; Nakaoka, H.; Kameoka, H. Biotransformation
of 1,8-cineole to (+)-2-endo-hydroxy-1,8-cineole by Glomer-
ella cingulata. Chem. Express 1991, 6 (9), 667-670.
Metabolites 5 and 6 were previously obtained on the
biotransformation of 4 by other microorganisms (5:
Abraham et al., 1989; Abraham and Stumpf, 1987;
Madyastha and Gurura, 1993; 6: Abraham et al., 1989;
J uttner and Hans, 1986); however, 7-9 had not been
obtained on the biotransformation of 4 by other micro-
organisms. In this system, similarly to 1, hydration at
the remote double bond of 4 was the main metabolic
pathway. Hydration at the remote double bond is a
characteristic metabolic pathway on the microbial trans-
formation of 1 and 4 by G. cingulata.
As shown in Table 1, in the case of 1 and 3 (trans-
form), hydration of the remote double bond was the
main pathway, while in the cases of 10 and 12 (cis-
form), oxidation of the remote double bond was the main
pathway, giving vic-diol (Miyazawa et al., 1995). These
differences in product formation by G. cingulata with
the trans-form (1 and 4) and the cis-form (10 and 12)
may be explained by the influence of the cis/trans
configuration of these substrates. So far, there is no
report of a clear distinction between the microbial
transformation of the trans-form (1 and 3) and that of
the cis-form (10 and 12). In other words, G. cingulata
recognized the cis/trans configuration on the microbial
transformation of 1, 4, 10, and 12.
Miyazawa, M.; Uemura, T.; Kameoka, H. Biotransformation
of (-)-globulol and (+)-ledol by Glomerella cingulata. Phy-
tochemistry 1994, 37 (4), 1027-1030.
Miyazawa, M.; Nankai, H.; Kameoka, H. Biotransformation
of (-)-R-bisabolol by plant pathogenic fungus, Glomerella
cingulata. Phytochemistry 1995a , 39 (5), 1077-1080.
Miyazawa, M.; Nankai, H.; Kameoka, H. Biotransformation
of (+)-cedrol by plant pathogenic fungus, Glomerella cin-
gulata. Phytochemistry 1995b, 40 (1), 69-72.
Miyazawa, M.; Nankai, H.; Kameoka, H. Biotransformations
of acyclic terpenoids, (()-cis-nerolidol and nerylacetone by
plant pathogenic fungus, Glomerella cingulata. Phytochem-
istry 1995c, 40 (4), 1133-1137.
Miyazawa, M.; Suzuki, Y.; Kameoka, H. Biotransformation of
(-)-nopol by Glomerella cingulata. Phytochemistry 1995d ,
39 (2), 337-340.
Miyazawa, M.; Yokote, K.; Kameoka, H. Resolution of racemic
linalool oxide-pyranoid by microbial esterification. Tetra-
hedron: Asymmetry 1995e, 6 (5), 1067-1068.
Tsuda, Y. Microbial reduction of naphthoxypropionic acids.
Chem. Pharm. Bull. 1987, 35 (6), 2554-2557.
Received for review J uly 19, 1995. Revised manuscript
received March 19, 1996. Accepted April 9, 1996.X This work
was supported in part by a Grant-in-Aid for Developmental
Scientific Research, the Ministry of Education, Science, and
Culture of J apan(40140305 to M.M.)
LITERATURE CITED
Abraham, W.-R.; Alfmann, H.-A. Addition of water to acyclic
terpenoids by Fusarium solani. Appl. Microbiol. Biotechnol.
1989, 32, 295-298.
Abraham, W.-R.; Stumpf, B. Enzymatic acyloin condensation
of acyclic aldehydes. Z. Naturforsch. 1987, 42C, 559-566.
J F950464U
X Abstract published in Advance ACS Abstracts, May
15, 1996.