title: A tale of four kingdoms - isoxazolin-5-one- and 3-nitropropanoic acid-derived natural products.
abstract: Covering up to September 2016This review reports on natural compounds that derive from the isoxazolinone ring as well as the 3-nitropropanoic acid (3-NPA) moiety. These structural elements occur in compounds that have been identified in plants, insects, bacteria and fungi. In particular, plants belonging to the family of legumes produce such compounds. In the case of insects, isoxazolin-5-one and 3-NPA derivatives were found in leaf beetles of the subtribe Chrysomelina. A number of these natural products have been synthesized so far. In the case of the single compound 3-NPA, several synthetic strategies have been reported and some of the most efficient routes are reviewed. The toxicity of 3-NPA results from its ability to bind covalently to the catalytic center of succinate dehydrogenase causing irreversible inhibition of mitochondrial respiration. As a motif that is produced by many species of plants, leaf beetles and fungi, different detoxification mechanisms for 3-NPA have evolved in different species. These mechanisms are based on amide formation of 3-NPA with amino acids, reduction to β-alanine, ester formation or oxidation to malonic acid semialdehyde. The biosynthetic pathways of 3-NPA and isoxazolin-5-one moieties have been studied in fungi, plants and leaf beetles. In the case of fungi, 3-NPA derives from aspartate, while leaf beetles use essential amino acids such as valine as ultimate precursors. In the case of plants, it is supposed that malonate serves as a precursor of 3-NPA, as indicated by feeding of14C-labeled precursors to Indigofera spicata. In other leguminous plants it is suggested that asparagine is incorporated into compounds that derive from isoxazolin-5-one, which was indicated by14C-labeled compounds as well. In the case of leaf beetles it was demonstrated that detection of radioactivity after14C-labeling from a few precursors is not sufficient to unravel biosynthetic pathways.
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Jena, Germany. boland@ice.mpg.de.
authors.forename: Tobias
authors.initials: T
authors.lastname: Becker
authors.affiliation: Department of Biology, Université Libre de Bruxelles, Brussels, Belgium.
authors.forename: Jacques
authors.initials: J
authors.lastname: Pasteels
authors.affiliation: Leibniz Institute for Natural Product Research and Infection Biology, Hans Knoell Institute, Jena, Germany.
authors.forename: Christiane
authors.initials: C
authors.lastname: Weigel
authors.affiliation: Leibniz Institute for Natural Product Research and Infection Biology, Hans Knoell Institute, Jena, Germany.
authors.forename: Hans-Martin
authors.initials: HM
authors.lastname: Dahse
authors.affiliation: Leibniz Institute for Natural Product Research and Infection Biology, Hans Knoell Institute, Jena, Germany.
authors.forename: Kerstin
authors.initials: K
authors.lastname: Voigt
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Jena, Germany. boland@ice.mpg.de.
authors.forename: Wilhelm
authors.identifier: 0000-0001-6784-2534
authors.initials: W
authors.lastname: Boland
mesh_terms: D000818:Animals; D001688:Biological Products / Q000737:chemistry* / Q000302:isolation & purification; D007555:Isoxazoles / Q000737:chemistry* / Q000302:isolation & purification; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry* / Q000302:isolation & purification; D011422:Propionates / Q000737:chemistry* / Q000302:isolation & purification
chemical_list: D001688:Biological Products; D007555:Isoxazoles; D009574:Nitro Compounds; D011422:Propionates; C013076:isoxazolin-5-one; C015392:3-nitropropionic acid