Enantioselective Microbial Hydroxylation as a Useful Tool in the Production of Jasmonate Derivatives with Aphid Deterrent Activity Anna Gliszczyn ´ska 1 • Witold Gladkowski 1 • Katarzyna Dancewicz 2 • Beata Gabrys ´ 2 Received: 3 February 2015 / Accepted: 2 April 2015 Ó Springer Science+Business Media New York 2015 Abstract Microbial transformations of two natural com- pounds dihydrojasmone (1) and cis-jasmone (3) in the growing cultures of selected twenty strains have been in- vestigated. The studies have demonstrated a biocatalytic potential of tested microorganisms for the enantioselective hydroxylation of jasmonates. The substrates underwent an effective regio- and stero-selective hydroxylation at the allylic position in the cyclopentenone ring, and the corre- sponding optically pure keto-alcohols (2, 4) were obtained. The process of biohydroxylation depended on the compo- sition of reaction medium. In the studied cultures, (?)-(R)- 4-hydroxydihydrojasmone (2) and (?) and (-)-4-hy- droxyjasmone (4a, 4b) were produced in good yields and high enantiomeric excesses. Moreover, the introduction of the hydroxy group into the molecule of jasmonate ketones 1 and 3 leads to biologically active derivatives 2 and 4 that regulate the behaviour of aphids Myzus persicae by ter- mination of their feeding. Introduction The term ‘jasmonates’ includes methyl jasmonate (MeJA), jasmonic acid (JA), cis-jasmone, their isomers, and ana- logues. It is a large family of natural organic compounds widespread in plants and some fungi [3, 9, 13, 22, 24, 35]. Up to now, jasmonates have been found in 206 plant species that belong to 160 families. (-)-(3R,7R)-MeJA was isolated for the first time in 1962 from the essential oil of Jasminum grandiflorum [10]. Its occurrence has been also confirmed in Rosmarinus officinalis by Crabalon et al. [6]. Pure (-)-JA was isolated first from the fungal culture of Botryodiplodia (syn. Lasiodiplodia) theobromae in 1971 [1]. A crucial element of the structure of jasmonates is the cyclopentane ring with two substituents at C-3 and C-7 and carbonyl group at C-6 (Fig. 1). Two stereogenic centres located at the carbon atoms C-3 and C-7 in this group of compounds determine the possibility of occurrence of four stereoisomers. Hill and Edwards in 1965 determined the configuration of natural (-)-MeJA as (3R,7R), with trans- oriented substituents at stereogenic centres [19]. Isomer cis is less stable because of forming an enol at C-7 that easily converts to MeJA. Therefore, (-)-(3R,7R)-MeJA and (?)- (3R,7S)-methyl epijasmonate occur in nature in a ratio of 97:3 as the odorous components of jasmine flower oil J. grandiflorum L. Two other stereoisomers were obtained as the products of chemical synthesis [7, 23]. The biological activity of MeJA obtained form Artemi- sia absinthium L. was described in the 1980s by Ueda and Kato [33]. These authors described the senescence-pro- moting effect of JA and characterized these compounds as plant growth inhibitors [8, 33]. Over past 50 years, our understanding of the role of jasmonates in plant growth, development, and defence has developed rapidly [4, 26, 31]. First of all, jasmonates act as endogenous growth regulators that control plant development, including seed germination, pollen development, ethylene synthesis, se- nescence, and tuber formation, through regulation of many physiological processes on the morphological, molecular, and cellular levels [11, 29, 30, 34]. Furthermore, they play a significant cell-signalling role in the defence responses of & Anna Gliszczyn ´ska anna.gliszczynska@wp.pl 1 Department of Chemistry, Wroclaw University of Environmental and Life Sciences, Norwida 25, 50-375 Wroclaw, Poland 2 Department of Biology and Ecology, University of Zielona Go ´ra, Szafrana 1, 65-516 Zielona Go ´ra, Poland 123 Curr Microbiol DOI 10.1007/s00284-015-0831-9