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... The ability of [1,2,3]triazolobenzoxazinones to act as a source of “hidden” diazo group was discovered. These diazo precursors can be easily prepared by the intramolecular cyclization of 2-(5-iodo-1,2,3-triazolyl)benzoic acids. The Cu-catalyzed capture of the hidden diazo group allows for further functionalization through the denitrogenative pathway. The transformations proceed via the formation o ...
... Cover crops provide many agroecosystem services, including weed suppression, which is partially exerted through release of allelopathic benzoxazinoid (BX) compounds. This research (1) characterizes changes in concentrations of BX compounds in shoots, roots, and soil at three growth stages (GS) of cereal rye (Secale cereale L.), and (2) their degradation in soil over time following termination. Con ...
Datasets:
Data from: Benzoxazinoids in roots and shoots of cereal rye (Secale cereale) and their fates in soil after cover crop termination
M. Iftikhar Hussain; Fabrizio Araniti; Margot Schulz; Scott Baerson; Yedra Vieites-Álvarez; Leonidas Rempelos; Paul Bilsborrow; Nuria Chinchilla; Francisco A. Macías; Leslie A. Weston; Manuel J. Reigosa; Adela M. Sánchez-Moreiras
... Allelopathic activity of wheat (Triticum aestivum L.) has previously been associated with the production of phenolic acids and flavonoids (PAF), benzoxazinones (BXZs) and phenoxazinones (PXZs). The biosynthesis of BXZs is closely regulated during cereal growth, with accumulation highest in young tissues with variation associated with genotype and environmental conditions. This review is focused on ...
... Gold(I)-catalyzed heteroannulation affords the efficient and straightforward construction of heterocyclic compounds. Herein, we developed a gold(I)-catalyzed heteroannulation of salicylic amides with alkynes producing a broad range of 1,3-benzoxazin-4-ones. The utility of this protocol was highlighted by synthesizing variously substituted benzoxazinones containing quaternary carbon centers, showin ...
... Plants compete with their neighbors about the limited resources available to them. Plants under induced stress resulting from competition may alter their metabolome to increase their resilience or enhance their defense mechanisms. In the present study, rye (Secale cereale) plants were cocultivated with different densities (3, 12, and 18 plants per pot) of Austrian pea (Pisum sativum subsp. arvense ...
... Fusarium crown rot (FCR), caused by Fusarium spp., is a chronic and severe plant disease worldwide. In the last years, the incidence and severity of FCR in China has increased to the point that it is now considered a threat to local wheat crops. In this study, for the first time, the metabolites and transcripts responsive to FCR infection in the partial resistant wheat cultivar 04 Zhong 36 (04z36) ...
... The highly enantioselective transfer hydrogenation of benzoxazinones with chiral phosphoric acids under H₂ was successfully achieved, where boranes promoted the hydrogenation of phenanthridine for the regeneration of dihydrophenanthridine as the hydrogen donor. A variety of dihydrobenzoxazinones were obtained in high yields with up to 99% ee. The current work provides a promising solution to unrea ...
... BACKGROUND: Plants growing in proximity to other plants are exposed to a variety of metabolites that these neighbors release into the environment. Some species produce allelochemicals to inhibit growth of neighboring plants, which in turn have evolved ways to detoxify these compounds. RESULTS: In order to understand how the allelochemical-receiving target plants respond to chemically diverse compo ...
ambient temperature; benzoxazinoids; electrochemistry; electrosynthesis; green chemistry; hydrazides; quinolines; regioselectivity
Abstract:
... An electrochemical protocol for the synthesis of 2,3-disubstituted quinolines by reacting benzoxazinones with arylsulfonyl hydrazides was established under simple and mild conditions (room temperature and an undivided cell). The methodology does not require noble catalysts or external oxidants, providing a green and mild pathway for de novo synthesis of functional quinolines with excellent regiose ...
... In maize (Zea mays ssp. mays), agriculturally damaging herbivores include lepidopteran insects, such as the European corn borer (Ostrinia nubilalis), and distantly related arthropods, like the two‐spotted spider mite (Tetranychus urticae). A small number of maize lines, including B96 and B75, are highly resistant to both herbivores, and B96 is also resistant to thrips. Using T. urticae as a repres ...
Aleksej Abramov; Thomas Hoffmann; Timo D. Stark; Linlin Zheng; Stefan Lenk; Richard Hammerl; Tobias Lanzl; Corinna Dawid; Chris-Carolin Schön; Wilfried Schwab; Alfons Gierl; Monika Frey
... Plant specialised metabolites constitute a layer of chemical defence. Classes of the defence compounds are often restricted to a certain taxon of plants, e.g. benzoxazinoids (BX) are characteristically detected in grasses. BXs confer wide-range defence by controlling herbivores and microbial pathogens and are allelopathic compounds. In the crops maize, wheat and rye high concentrations of BXs are ...
Eriochloa villosa; agronomy; annual weeds; benzoxazinoids; germination; invasive species; East Asia; Europe; North America
Abstract:
... Woolly cupgrass (Eriochloa villosa Thunb. Knuth) is a common weed which is native to East Asia. It also was introduced into North America and Europe. The problems related to controlling this annual weed are due to its germination characteristics, low susceptibility to certain herbicides and considerable competitiveness against other plant species. Several genera of the Panicoideae subfamily contai ...
... Benzoxazinoids are a class of protective and allelopathic plant secondary metabolites that have been identified in multiple grass species and are encoded by the Bx biosynthetic gene cluster (BGC) in maize. Data mining of 41 high-quality grass genomes identified complete Bx clusters (containing genes Bx1–Bx5 and Bx8) in three genera (Zea, Echinochloa, and Dichanthelium) of Panicoideae and partial c ...
... The maize (Zea mays) genome encodes three indole‐3‐glycerolphosphate synthase enzymes (IGPS1, 2, and 3) catalyzing the conversion of 1‐(2‐carboxyphenylamino)‐l‐deoxyribulose‐5‐phosphate to indole‐3‐glycerolphosphate. Three further maize enzymes (BX1, benzoxazinoneless 1; TSA, tryptophan synthase alpha subunit; and IGL, indole glycerolphosphate lyase) convert indole‐3‐glycerolphosphate to indole, w ...
... Despite the scientific and economic importance of maize, little is known about its specialized metabolism. Here, five maize organs were profiled using different reversed-phase liquid chromatography-mass spectrometry methods. The resulting spectral metadata, combined with candidate substrate-product pair (CSPP) networks, allowed the structural characterization of 427 of the 5,420 profiled compounds ...
Lewis bases; alcohols; benzoxazinoids; carbamates; enantioselectivity; oxidation
Abstract:
... The utilization of the Bpin group as a pronucleophile to facilitate the assembly of cyclic carbamates has been achieved. This one-pot process involves an initial copper-catalyzed borylation, a subsequent C–B bond oxidation to generate the reactive alcohol intermediate, and a cyclization. We report the use of this efficient, scalable, and simple method toward the synthesis of a wide range of benzox ...
... Entomopathogenic fungi (EPF) can display a plant‐associated lifestyle as endophytes. Seed application of EPF can affect insect herbivory above ground, but the mechanisms behind this are not documented. Here we applied three EPF isolates, Beauveria bassiana, Metarhizium brunneum and M. robertsii, as seed inoculation of wheat and bean, and evaluated the effects on population growth of aphids, Rhopal ...
Selma Cadot; Valentin Gfeller; Lingfei Hu; Nikhil Singh; Andrea Sánchez‐Vallet; Gaétan Glauser; Daniel Croll; Matthias Erb; Marcel G. A. van der Heijden; Klaus Schlaeppi
... Plant–soil feedbacks refer to effects on plants that are mediated by soil modifications caused by the previous plant generation. Maize conditions the surrounding soil by secretion of root exudates including benzoxazinoids (BXs), a class of bioactive secondary metabolites. Previous work found that a BX‐conditioned soil microbiota enhances insect resistance while reducing biomass in the next generat ...
... INTRODUCTION: Benzoxazinoids (BXs) are plant phytochemicals that have both defensive properties in plants and therapeutic effects in humans. The presence of BXs has been largely studied in the Poaceae family (monocots). To study the presence or absence of BXs in dicotyledons and monocotyledons outside the Poaceae family, parts of 24 plant species at several growth stages were selected for analysis ...
... An efficient iridium-catalyzed enantioselective hydrogenation of 2-alkylidene 1,4-benzoxazin-3-ones using our developed iPr-BiphPHOX as a ligand is reported. This method showed good functional group compatibility and delivered the corresponding reduced products in excellent yields (up to 99%) with excellent enantioselectivities (up to 99% ee). The reaction proceeded very well on a gram scale with ...
... In order to cope with the presence of unfavorable compounds, plants can biotransform xenobiotics, translocate both parent compounds and metabolites, and perform compartmentation and segregation at the cellular or tissue level. Such a scenario also applies to mycotoxins, fungal secondary metabolites with a pre‐eminent role in plant infection. In this work, we aimed to describe the effect of the int ...
... BACKGROUND: Common purslane (Portulaca oleracea) and annual ryegrass (Lolium rigidum) are important infesting weeds of field crops. Herbicides are mostly used for weed suppression, while their environmental toxicity and resistance in weeds against them demand considering alternative options, such as the use of allelopathic crops for weed management. Wheat is an important allelopathic crop and pres ...
... 2,4‐Dihydroxy‐7‐methoxy‐1,4‐benzoxazin‐3‐one (DIMBOA) and DIMBOA‐glucoside (DIMBOA‐Glc) are anti‐insect benzoxazinoids in maize, yet very little information is known about how they are regulated. Reverse genetics, kinase activity analysis, phytohormone and DIMBOA/DIMBOA‐Glc quantification, bioassays and transcriptome analysis were employed to study the function of ZmMPK6, a mitogen‐activated prote ...
... Transition metal-catalyzed cycloaddition has been established as a powerful tool for heterocycle synthesis. Despite impressive advances, the exploitation of new catalysis strategies and systems is still highly significant to enrich the heterocycle family. Herein, we disclosed a cooperative catalysis system merging an achiral Pd catalyst and a chiral Co catalyst for the asymmetric [4+2] cycloadditi ...
... Benzoxazinoids are plant specialized metabolites with defense properties, highly abundant in wheat (Triticum), one of the world’s most important crops. The goal of our study was to characterize dioxygenase BX6 genes in tetraploid and hexaploid wheat genotypes and to elucidate their effects on defense against herbivores. Phylogenetic analysis revealed four BX6 genes in the hexaploid wheat T. aestiv ...
... Allelopathy is a biochemical interaction between plants in which a donor plant releases secondary metabolites, allelochemicals, that are detrimental to the growth of its neighbours. Traditionally considered as bilateral interactions between two plants, allelopathy has recently emerged as a cross-kingdom process that can influence and be modulated by the other organisms in the plant’s environment. ...
Triticum aestivum; alkylresorcinols; antioxidant activity; benzoxazinoids; cultivars; free radicals; health promotion; phytochemicals; spring; value added; winter wheat; Poland
Abstract:
... The health-promoting properties of the grains of common wheat (Triticum aestivum L.) are associated with the presence of unique phytochemicals. This study determines the profile of alkylresorcinols (ARs) and benzoxazinoids (BXs) in T. aestivum spring and winter cultivars grown in Poland under the two different production systems: conventional and organic. Wheat grain extracts were subjected to qua ...
... Benzoxazinoids (BXs) are specialized metabolites with protective properties that are synthesized predominantly by Poaceae species, including rye (Secale cereale). Among factors known to influence BXs production, prolonged low temperature has not been studied previously. In this study, the influence of cultivation at 4 °C, which is essential for vernalization, on the concentration of BXs (HBOA, DIB ...
NAD (coenzyme); NADP (coenzyme); benzoxazinoids; biomimetics; catalysts; chemical reactions; enantioselectivity; hydrogen bonding; models
Abstract:
... Using ureas as transfer catalysts through hydrogen bonding activation, biomimetic asymmetric reduction of benzoxazinones and quinoxalinones with chiral and regenerable NAD(P)H models was described, giving chiral dihydrobenzoxazinones and dihydroquinoxalinones with high yields and excellent enantioselectivities. A key dihydroquinoxalinone intermediate of a BRD4 inhibitor was synthesized using biomi ...
... Benzoxazinoids (BXs) are secondary metabolites synthesized mainly by gramineous plants, including rye (Secale cereale L.), that play an important role in stress resistance and allelopathy. In the present work, the influence of cocultivation of rye with berseem clover (Trifolium alexandrinum L.) on the expression of BX synthesis‐regulating genes (ScBx1–ScBx5, ScIgl, and ScGT) and the content of six ...
... We report an unexpected rearrangement of 3-hydroxyoxindoles into benzoxazinones using electrochemistry. Our reaction employs mild and environmentally friendly conditions, and the benzoxazinone products are obtained in moderate to excellent yields. Mechanistic experiments suggest that a peroxide intermediate is likely involved. ...
... Alternative strategies to control weeds are required at the field level to reduce herbicides and derived pollution. As cover crop, rye (Secale cereale L.) is adopted mainly because of its allelopathic weed control, which takes place through a strong inhibition of germination and seedling growth in several types of grass and broad-leaved weeds. The present study consisted of: i) a field trial, focu ...
... Benzoxazinoids (BXs) are plant secondary metabolites, first discovered in the 1950s, which are synthesized in many monocotyledonous species from the Poaceae family and in several dicotyledonous plants. They constitute a significant element of the plant’s defence mechanism against both biotic (pests and diseases) and abiotic (elevated salinity, heavy metals) stresses. The aim of this research was t ...
Nataliya Bilyera; Xuechen Zhang; Patrick Duddek; Lichao Fan; Callum C. Banfield; Steffen Schlüter; Andrea Carminati; Anders Kaestner; Mutez A. Ahmed; Yakov Kuzyakov; Michaela A. Dippold; Sandra Spielvogel; Bahar S. Razavi
... Plants stimulate microbial enzyme production in the rhizosphere, regulating soil organic matter decomposition and nutrient cycling. The availability of labile organic compounds (i.e. exudates) and water is the main prerequisite for such microbial activity and enzyme production, thus shaping the rhizosphere. Root morphology (i.e., root hairs) and exudate composition define the spatial distribution ...
benzoxazinoids; environment; mass spectrometry; metabolites; metabolomics; rye; weeds
Abstract:
... Translocation of metabolites between different plant species provides important hints in understanding the fate of bioactive root exudates. In the present study, targeted and untargeted mass spectrometry‐based metabolomics was applied to elucidate the transfer of bioactive compounds between rye and several crops and weed species. Our results demonstrated that benzoxazinoids (BXs) synthesized by ry ...
... BACKGROUND AND OBJECTIVES: Integrated weed management in commercial wheat production is urgently needed due to increasing herbicide resistance and production costs. Benzoxazinoids (BXs), which include benzoxazinones and benzoxazolinones, are unique bioactive metabolites produced by certain members of the Poaceae including maize, wheat, rye and some dicots. BXs play important roles in plant defence ...
... The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinon ...
... Beneficial rhizobacteria can inhibit foliar pathogen infection by activation of defense responses, yet it the mechanisms of rhizobacteria-induced disease resistance remain largely unknown. Here, inoculation of susceptible maize plants with Pseudomonas fluorescens MZ05 significantly reduced disease occurrence caused by the leaf pathogen Setosphaeria turcica. Gene expression profiles of MZ05-inocula ...
Secale cereale; Vicia villosa; benzoxazinoids; chemical analysis; chemical defenses; coculture; exudation; food chemistry; rapid methods; rhizosphere; root exudates; rye; tandem mass spectrometry
Abstract:
... Plants have evolved advanced chemical defense mechanisms, including root exudation, which enable them to respond to changes occurring in their surroundings rapidly. Yet, it remains unresolved how root exudation affects belowground plant–plant interactions. The objective of this study was to elucidate the fate of benzoxazinoids (BXs) exuded from the roots of rye (Secale cereale L.) plants grown wit ...
... The direct functionalization of N-heterocycles is a vital transformation for the development of pharmaceuticals, functional materials, and other chemical entities. Herein, the transition-metal-free alkylation and acylation of C(sp²)–H bonds in biologically relevant 2-benzoxazinones with 1,4-dihydropyridines as readily accessible radical surrogates is described. Excellent functional group compatibi ...
... Numerous allelopathic plant secondary metabolites impact plant–microorganism interactions by injuring plant-associated beneficial bacteria and fungi. Fungi belonging to the genus Trichoderma positively influence crops, including benzoxazinone-containing maize. However, benzoxazinones and their downstream metabolites such as benzoxazolinone and phenoxazinones are often fungitoxic. Specimen Trichode ...
... BACKGROUND: Young wheat plants are continuously exposed to herbivorous insect attack. To reduce insect damage and maintain their growth, plants evolved different defense mechanisms, including the biosynthesis of deterrent compounds named benzoxazinoids, and/or trichome formation that provides physical barriers. It is unclear whether both of these mechanisms are equally critical in providing an eff ...
Florent D. Lavergne; Corey D. Broeckling; Kitty J. Brown; Darren M. Cockrell; Scott D. Haley; Frank B. Peairs; Stephen Pearce; Lisa M. Wolfe; Courtney E. Jahn; Adam L. Heuberger
... Common wheat (Triticum aestivum L.) is a global staple crop, and insect pests can impact grain yield. The wheat stem sawfly (Cephus cinctus, WSS) is a major wheat pest, and while partial resistance has been deployed by breeding for a solid-stem trait, this trait is affected by environment. Here, a proteomics and metabolomics study was performed on four wheat cultivars to characterize a molecular r ...
... The plant O-methyltransferases are dependent on S-Adenosyl-l-methionine, which can catalyze a variety of secondary metabolites. Here we identified different number of OMT genes from the respective grass genomes. Phylogenetic analysis showed that this OMT gene family is a grass-specific gene family that is different from COMT. Most of genes were expanded by tandem and segment duplication after the ...
... Inorganic phosphorus (Pi) is an essential element in numerous metabolic reactions and signaling pathways, but the molecular details of these pathways remain largely unknown. In this study, metabolite profiles of maize (Zea mays L.) leaves and roots were compared between six low‐Pi‐sensitive lines and six low‐Pi‐tolerant lines under Pi‐sufficient and Pi‐deficient conditions to identify pathways and ...
... Little is known regarding insect defense pathways in Setaria viridis (setaria), a model system for panicoid grasses, including Zea mays (maize). It is thus of interest to compare insect herbivory responses of setaria and maize. Here we use metabolic, phylogenetic, and gene expression analyses to measure a subset of jasmonic acid (JA)-related defense responses to leaf-chewing caterpillars. Phylogen ...
... BACKGROUND: Insect herbivory poses a major threat to maize. Benzoxazinoids are important anti-insect secondary metabolites in maize, whose biosynthetic pathway has been extensively studied. However, yet little is known about how benzoxazinoids are regulated in maize, partly due to lack of mutant resources and recalcitrance to genetic transformation. Transient systems based on mesophyll- or culture ...
... BACKGROUND AND AIMS: Although aluminum (Al) exclusion via root exudation of organic matters is a common resistance mechanism adopted by many plant species, whether root exudation of benzoxazinoids, such as hydroxamic acids (HAs), confers Al resistance remains unclear. METHODS: We performed physiological characterization for an Al-resistant maize cultivar TY and a sensitive maize cultivar ZD. RESUL ...
Suresh Varsani; Sajjan Grover; Shaoqun Zhou; Kyle G. Koch; Pei-Cheng Huang; Michael V. Kolomiets; W. P. Williams; Tiffany Heng-Moss; Gautam Sarath; Dawn S. Luthe; Georg Jander; Joe Louis
... The corn leaf aphid (CLA; Rhopalosiphum maidis) is a phloem sap-sucking insect that attacks many cereal crops, including maize (Zea mays). We previously showed that the maize inbred line Mp708, which was developed by classical plant breeding, provides enhanced resistance to CLA. Here, using electrophysiological monitoring of aphid feeding behavior, we demonstrate that Mp708 provides phloem-mediate ...
... The Asian corn borer (Ostrinia furnacalis Guenée) is a destructive pest of maize (Zea mays L.). Despite large‐scale commercial maize production, little is known about the defensive responses of field‐grown commercial maize to O. furnacalis herbivory, and how these responses result in direct and indirect defence against this pest. To elucidate the maize transcriptome response to O. furnacalis feedi ...