Transformation of (±)-lavandulol and (±)-tetrahydrolavandulol by a fungal strain Rhizopus oryzae
Highlights
► Biotransformation of lavandulol and tetrahydrolavandulol studied using Rhizopus oryzae. ► Five metabolites isolated and characterized with lavandulol. ► Two metabolites isolated and characterized with tetrahydrolavandulol. ► R. oryzae efficiently carried out hydroxylation and epoxidation.
Introduction
The irregular monoterpene alcohol, lavandulol is a constituent of essential oils and also an important additive in perfumery and cosmetic industry (Schinz and Schappi, 1947, Seino et al., 2008, Simon et al., 1946, Soucek and Dolejs, 1959). Homochiral lavandulol exists naturally in its (R)-form in the essential oil of lavender. The esters of both (R)- and (S)-lavandulol are the segregation pheromones of insects such as Anthonomus rubi Herbst (Innocenzi et al., 2001) and Planococcus ficus, (Zada et al., 2003, Zada et al., 2008), respectively. (R)-lavandulyl-(S)-methylbutanoate is a component of female sex pheromone of the hibiscus mealybug (Zhang et al., 2004) whereas (R)-lavandulyl acetate is a component of the male sex pheromone of the western flower thrips (Hamilton et al., 2005). (R)-lavandulol is being synthesized in nature by the condensation of two molecules of dimethylallyldiphosphate (DMAPP) and the mechanism of formation of (R)-lavandulol is well documented (SD, Fig. S1) (Thulasiram et al., 2007). 1′-2 Irregular monoterpene, (R)-lavandulol was formed through dissociative electrophilic alkylation of the double bond in DMAPP by the dimethylallyl carbocation (DMA+) to give cyclopropyl carbocation. The cyclopropyl carbocation formed after rearrangement yield lavandulyl carbocation which in turn will be deprotonated to yield lavandulyl diphosphate (SD, Fig. S1) (Thulasiram et al., 2007, Thulasiram et al., 2008). Although considerable work has been carried out on the biosynthesis of lavandulol, very little is known regarding the biotransformation of this irregular monoterpene alcohol. Therefore, it is of great interest to know the mode of biotransformation of lavandulol and tetrahydrolavandulol as they are being used extensively in perfumery and cosmetic industry. This study describes the biotransformation of racemic lavandulol (I) and its tetrahydro-derivative (II) by a soil isolated fungal strain Rhizopus oryzae. In fact, R. oryzae is more versatile in its ability to transform lavandulol compared to the fungus tested earlier (Nankai et al., 1997, Nankai et al., 1998). Five metabolites for I and two metabolites for II from fermentation medium were isolated and characterized.
Section snippets
Chemicals and reagents
Lavandulol was purchased from Sigma–Aldrich. Media ingredients, salts and acids were purchased from HiMedia Laboratories, Mumbai, India. Tetrahydrolavandulol was purchased from ABCR GmbH & Co KG, Germany.
Microorganism
The microorganism used in the present study was isolated from soil collected underneath eucalyptus tree. The organism was maintained and propagated on potato dextrose agar slants. The fungal strain used in the study was identified by sequencing ITS1 and ITS2 region, it showed best match with R.
Results and discussion
To investigate the biotransformation of I and II, 30 fungal systems were screened. The GC and GC–MS analyses of the crude extract after incubating three days of I and II revealed that the soil isolated fungal strain R. oryzae efficiently transformed both I and II into corresponding oxygenated metabolites. All other fungal systems did not produce noticeable transformation for the isolation and characterization of metabolites. Hence, R. oryzae was selected for biotransformation study of I and II.
Conclusion
The soil isolated fungal system R. oryzae has a potential to hydroxylate at allylic positions or at tertiary positions or carryout epoxidation of the double bonds on acyclic monoterpenoids, lavandulol (I) and tetrahydrolavandulol (II) in a highly efficient manner to produce various hydroxylated derivatives of I and II which might be useful in pheromone components, perfumes and cosmetics.
Acknowledgements
P.D. thanks CSIR-New Delhi for fellowship. H.V.T. is grateful for the encouragement of Dr. S. Sivaram, Dr. B.D. Kulkarni, and Dr. Girish Sahni. This work was supported by CSIR Network grant and the Director, NCL, Pune.
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