title: Synthesis, structural characterization and biological activity of two diastereomeric JA-Ile macrolactones.
abstract: Jasmonates are phytohormones involved in a wide range of plant processes, including growth, development, senescence, and defense. Jasmonoyl-L-isoleucine (JA-Ile, 2), an amino acid conjugate of jasmonic acid (JA, 1), has been identified as a bioactive endogenous jasmonate. However, JA-Ile (2) analogues trigger different responses in the plant. ω-Hydroxylation of the pentenyl side chain leads to the inactive 12-OH-JA-Ile (3) acting as a “stop” signal. On the other hand, a lactone derivative of 12-OH-JA (5) (jasmine ketolactone, JKL) occurs in nature, although with no known biological function. Inspired by the chemical structure of JKL (6) and in order to further explore the potential biological activities of 12-modified JA-Ile derivatives, we synthesized two macrolactones (JA-Ile-lactones (4a) and (4b)) derived from 12-OH-JA-Ile (3). The biological activity of (4a) and (4b) was tested for their ability to elicit nicotine production, a well-known jasmonate dependent secondary metabolite. Both macrolactones showed strong biological activity, inducing nicotine accumulation to a similar extent as methyl jasmonate does in Nicotiana attenuata leaves. Surprisingly, the highest nicotine contents were found in plants treated with the JA-Ile-lactone (4b), which has (3S,7S) configuration at the cyclopentanone not known from natural jasmonates. Macrolactone (4a) is a valuable standard to explore for its occurrence in nature.
authors: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knoell-Straße 8, 07745 Jena, Germany. boland@ice.mpg.de.
authors: Guillermo H
authors: GH
authors: Jimenez-Aleman
authors: Ricardo A R
authors: RA
authors: Machado
authors: Helmar
authors: H
authors: Görls
authors: Ian T
authors: IT
authors: Baldwin
authors: Wilhelm
authors: W
authors: Boland
mesh_terms: D018360:Crystallography, X-Ray; D003517:Cyclopentanes / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D007532:Isoleucine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D031660:Jasminum / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D009538:Nicotine / Q000378:metabolism; D018515:Plant Leaves / Q000378:metabolism; D013237:Stereoisomerism; D014026:Nicotiana / Q000378:metabolism
chemical_list: D003517:Cyclopentanes; D007783:Lactones; C532883:jasmonoyl-isoleucine; D007532:Isoleucine; D009538:Nicotine