Volatiles from the tropical ascomycete Daldinia clavata (Hypoxylaceae, Xylariales)

• Tao Wang,
• Kathrin I. Mohr,
• Marc Stadler and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2018, 14, 135–147, doi:10.3762/bjoc.14.9

• widespread fungal volatile is 6-pentyl-2H-pyran-2-one (2) that was first isolated from Trichoderma and exhibits a strong coconut aroma [5]. For fungi producing 2 a plant-growth promoting effect and an induction of systemic resistance in plants has been observed which makes these fungi interesting as

Aminomethylation/hydrogenolysis as an alternative to direct methylation of metalated isoquinolines – a novel total synthesis of the alkaloid 7-hydroxy-6-methoxy-1-methylisoquinoline

• Benedikt C. Melzer,
• Jan G. Felber and
• Franz Bracher

Beilstein J. Org. Chem. 2018, 14, 130–134, doi:10.3762/bjoc.14.8

• considerable relevance in drug development, since it is found in both complex [1] and “simple” alkaloids (variously substituted derivatives of the native isoquinoline) isolated from different plants [2], and antiviral and antimicrobial activities have been found for numerous isoquinoline alkaloids [3]. Further

Aminosugar-based immunomodulator lipid A: synthetic approaches

• Alla Zamyatina

Beilstein J. Org. Chem. 2018, 14, 25–53, doi:10.3762/bjoc.14.3

• response in plants during symbiosis in root cells. Additionally, certain Rhizobium sin-1 lipid A isolates were shown to inhibit the LPS induced toxic effects in human immune cells [115]. To determine the structural features which are responsible for the LPS antagonizing properties of the heterogeneous

A concise flow synthesis of indole-3-carboxylic ester and its derivatisation to an auxin mimic

• Marcus Baumann,
• Ian R. Baxendale and
• Fabien Deplante

Beilstein J. Org. Chem. 2017, 13, 2549–2560, doi:10.3762/bjoc.13.251

• pharmaceuticals [1][2][3][4]. Indoles also play a significant role as phytohormones that promote and regulate the growth and development of plants. Indeed, four of the five endogenously synthesised auxins produced by plants contain the indole motif (Figure 1, structures 3–7). As a consequence of their regulatory

Herpetopanone, a diterpene from Herpetosiphon aurantiacus discovered by isotope labeling

• Xinli Pan,
• Nicole Domin,
• Sebastian Schieferdecker,
• Hirokazu Kage,
• Martin Roth and
• Markus Nett

Beilstein J. Org. Chem. 2017, 13, 2458–2465, doi:10.3762/bjoc.13.242

• resemblance to cadinane-type sesquiterpenes from plants, but is structurally entirely unprecedented in bacteria. Based on its molecular architecture, a possible biosynthetic pathway is postulated. Keywords: genome mining; herpetopanone; Herpetosiphon; isotope labeling; terpene; Introduction Terpenoids

• were mainly reported from plants and, to a lesser degree, also from fungi and marine invertebrates. In recent years, however, the discovery of terpenoids from prokaryotes has gained momentum. The ease of DNA sequencing has strongly favored this development, contributing to the identification of

• , whereas a plant-derived sesquiterpene with this feature was already reported in 1965. Oplopanone (2, Figure 3) was originally isolated from Oplopanax japonicus [18][19], but can also be found in a number of other plants as well as red algae [20][21]. Comparison of the chemical shifts in 1 with published

Synthesis of ergostane-type brassinosteroids with modifications in ring A

• Vladimir N. Zhabinskii,
• Darya A. Osiyuk,
• Yuri V. Ermolovich,
• Natalia M. Chaschina,
• Tatsiana S. Dalidovich,
• Miroslav Strnad and
• Vladimir A. Khripach

Beilstein J. Org. Chem. 2017, 13, 2326–2331, doi:10.3762/bjoc.13.229

• moieties, exhibit hormonal activity in plants, whereas other BS are considered to be either biosynthetic precursors or metabolites of the “real” phytohormones [2]. All these compounds are part of a multidimensional biosynthetic metabolic network, the functioning of which is still far from being completely

Diosgenyl 2-amino-2-deoxy-β-D-galactopyranoside: synthesis, derivatives and antimicrobial activity

• Henryk Myszka,
• Patrycja Sokołowska,
• Agnieszka Cieślińska,
• Andrzej Nowacki,
• Maciej Jaśkiewicz,
• Wojciech Kamysz and
• Beata Liberek

Beilstein J. Org. Chem. 2017, 13, 2310–2315, doi:10.3762/bjoc.13.227

• the obtained compounds are active against Gram-positive bacteria and Candida type fungi. Keywords: antimicrobial activities; D-galactosamine; diosgenin; glycosylation; saponin; tetrachlorophthalimido derivatives; Introduction Saponins are steroid or triterpenoid glycosides found in various plants [1

• glycosides constitute a very important group among spirostanol saponins. Diosgenin has a double bond between the C-5 and C-6 atoms of the spirostanol skeleton and can be found in combination with different sugars in Costus, Discorea, Paris, Solanum, Yucca, and Trillium plants [11]. The plants containing

• directly bound with sapogenin are rarely found in plants, there are some examples of such galactosides. For example, timosaponin, isolated from an Anemarrhena asphodeloides plant, is a natural spirostanol saponin, which has D-galactose bound with sarsapogenin [15]. Tribulus plants are known to contain

New bio-nanocomposites based on iron oxides and polysaccharides applied to oxidation and alkylation reactions

• Daily Rodríguez-Padrón,
• Alina M. Balu,
• Antonio A. Romero and
• Rafael Luque

Beilstein J. Org. Chem. 2017, 13, 1982–1993, doi:10.3762/bjoc.13.194

• inexpensively produced by microbes, plants, and animals, and constitute a green alternative to synthetic polymers in the preparation of nanomaterials, in order to ameliorate environmental issues [34]. Therefore, one of the objectives of this work was to investigate the catalytic behavior of nanocomposites based

Enzymatic synthesis of glycosides: from natural O- and N-glycosides to rare C- and S-glycosides

• Jihen Ati,
• Pierre Lafite and
• Richard Daniellou

Beilstein J. Org. Chem. 2017, 13, 1857–1865, doi:10.3762/bjoc.13.180

• -glycosides have been described in literature [12][17][18]. Historically, glucosinolates have been the first identified S-glycosides for 50 years in cruciferous vegetables [19]. Along with the myrosinase GH enzyme, they are part of the “mustard bomb” system as a protective mechanism for plants against insect

• ]. More recently, BcGT1 from Bacillus subtilis was shown to efficiently catalyse the glucosylation of thiol-containing acceptors [32]. C-Glycosyltransferases For more than 50 years, C-glycosides have been identified in plants [33][34] as secondary metabolites. At least 5 families of aromatic aglycones

• have been reported to be C-glycosylated: flavones, xanthones, chromones, anthrones, and gallic acids. Several corresponding plant C-GT have been cloned, expressed and characterized, from several crops including maize [35], rice [36][37], wheat [36], buckwheat [38] and other plants such as Arabidopsis

18-Hydroxydolabella-3,7-diene synthase – a diterpene synthase from Chitinophaga pinensis

• Jeroen S. Dickschat,
• Jan Rinkel,
• Patrick Rabe,
• Arman Beyraghdar Kashkooli and
• Harro J. Bouwmeester

Beilstein J. Org. Chem. 2017, 13, 1770–1780, doi:10.3762/bjoc.13.171

• ) and the NSE triad NDXXSXX(R,K)(E,D), modified to a DTE triad in plants, for binding of the Mg2+ cofactor that forms a trinuclear (Mg2+)3 cluster to which the diphosphate portion of the substrate binds. Upon substrate binding the active site closes, resulting in hydrogen bonds between the substrate’s

• (−)-bornyl diphosphate synthases from the plants Salvia officinalis and Tanacetum vulgare forming a more polar product by the unusual termination via reattack of diphosphate [1], the trichodiene synthase from the fungus Trichothecium roseum [2], and pentalenene synthase from Streptomyces exfoliatus [3

• synthases in plants are targeted to the mitochondria [27], we decided to attempt the expression of HdS with mitochondrial targeting (HdS-mit). A construct without targeting signal (HdS; resulting in cytoplasmic localisation) and an empty vector were used as controls. A p19 construct [28] was co-infiltrated

A novel approach to oxoisoaporphine alkaloids via regioselective metalation of alkoxy isoquinolines

• Benedikt C. Melzer and
• Franz Bracher

Beilstein J. Org. Chem. 2017, 13, 1564–1571, doi:10.3762/bjoc.13.156

• bianfugecine (6) were isolated from Menispermum dauricum DC, among a few other plants [1][7][8]. A number of approaches to the oxoaporphine ring system has been published, typically involving the synthesis of 1-benzyl/1-benzoylisoquinoline intermediates, followed by cyclization under intramolecular biaryl

Glycoscience@Synchrotron: Synchrotron radiation applied to structural glycoscience

• Serge Pérez and
• Daniele de Sanctis

Beilstein J. Org. Chem. 2017, 13, 1145–1167, doi:10.3762/bjoc.13.114

• dynamics, plasticity of GTs and conformation changes that allow for substrate recognition and catalysis [37]. In plants, GTs are also involved in the biosynthesis of hemicellulose. Xyloglucan is one of the main hemicellulose components in the cell walls of dicots. Its biosynthesis involves different GTs

• to about 1,500. Interestingly, about 60% of them were obtained ligated to carbohydrates, which range from monosaccharides to 10 residue-long oligosaccharides. Lectins occur in plants, animals, algae, bacteria, fungi and yeasts, and viruses. Their involvement in key biologically-important recognition

• processes is well documented, as in the case of embryogenesis, fertilization, inflammation and metastasis. Lectins play a key role in parasite-symbiotic recognition in microbes and invertebrates of plants and vertebrates. The present role assigned to lectin lies in their ability to decipher sugar-encoded

From chemical metabolism to life: the origin of the genetic coding process

• Antoine Danchin

Beilstein J. Org. Chem. 2017, 13, 1119–1135, doi:10.3762/bjoc.13.111

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic

• Chinmay A. Shukla and
• Amol A. Kulkarni

Beilstein J. Org. Chem. 2017, 13, 960–987, doi:10.3762/bjoc.13.97

• published work, patents, etc., by many folds. Automation is a powerful tool if used correctly, but can also be expensive if not utilized correctly [13]. Automation in chemical plants: The role of automation in chemical industries is to enhance the product quality, reduce the dependence on the availability

• industries have been experiencing growing demands for process automation services like hardware and standard software. Stephanopoulos has reviewed the process control approach in chemical plants in detail [52]. The process control system should be designed to achieve the control objectives which are

Use of costic acid, a natural extract from Dittrichia viscosa, for the control of Varroa destructor, a parasite of the European honey bee

• Kalliopi Sofou,
• Demosthenis Isaakidis,
• Apostolos Spyros,
• Anita Büttner,
• Athanassios Giannis and
• Haralambos E. Katerinopoulos

Beilstein J. Org. Chem. 2017, 13, 952–959, doi:10.3762/bjoc.13.96

• . It has been previously isolated from D. viscosa and its structure was confirmed via NMR analysis [36][37][38]. Moreover, D. viscosa is not the only species containing costic acid as a metabolite. It has been reported in the literature as a component in other plants such as Nectandra cissiflora, Nees

Opportunities and challenges for the sustainable production of structurally complex diterpenoids in recombinant microbial systems

• Katarina Kemper,
• Max Hirte,
• Markus Reinbold,
• Monika Fuchs and
• Thomas Brück

Beilstein J. Org. Chem. 2017, 13, 845–854, doi:10.3762/bjoc.13.85

• largest and most structurally diverse group of natural products. They are ubiquitous in bacteria, plants, animals and fungi, conducting several biological functions such as cell wall components or defense mechanisms. Industrial applications entail among others pharmaceuticals, food additives, vitamins

• isoprenoid titers in plants may be low in dependence to seasonal [9] or circadian expression [10]. On the other hand for some members simply the number of available plants may be limited like the pacific yew Taxus brevifolia from which paclitaxel was first extracted [11]. The chemical synthesis can be an

• plant diterpenes in well-established recombinant hosts, such as Escherichia coli [21][22][23]. Recent developments in this field will be reviewed in this work. Review Biosynthesis of diterpenes and transfer to heterologous production system Integration of biosynthetic gene clusters from plants into a

The effect of cyclodextrin complexation on the solubility and photostability of nerolidol as pure compound and as main constituent of cabreuva essential oil

• Joyce Azzi,
• Pierre-Edouard Danjou,
• David Landy,
• Steven Ruellan,
• Lizette Auezova,
• Hélène Greige-Gerges and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2017, 13, 835–844, doi:10.3762/bjoc.13.84

• (Ner, 3,7,11-trimethyl-1,6,10-dodecatrien-3-ol), an acyclic sesquiterpene obtained from fresh flowers of bitter orange and found in many other plants [1], is extensively used in perfumery. It was also approved by the U.S. Food and Drug Administration as a food flavoring agent and included by the

Nucleophilic and electrophilic cyclization of N-alkyne-substituted pyrrole derivatives: Synthesis of pyrrolopyrazinone, pyrrolotriazinone, and pyrrolooxazinone moieties

• Işıl Yenice,
• Sinan Basceken and
• Metin Balci

Beilstein J. Org. Chem. 2017, 13, 825–834, doi:10.3762/bjoc.13.83

• (Figure 1) [7][8]. Triazinone heterocycles are essential in organic synthesis regarding their herbicide, anticancer, antimicrobial, and antimetastatic activities. Metamitron (3) and metribuzin (4), 1,2,4-triazinone herbicides having an amino group, are absorbed by the roots of plants and inhibit

Isoxazole derivatives as new nitric oxide elicitors in plants

• Anca Oancea,
• Emilian Georgescu,
• Florentina Georgescu,
• Alina Nicolescu,
• Elena Iulia Oprita,
• Catalina Tudora,
• Lucian Vladulescu,
• Marius-Constantin Vladulescu,
• Florin Oancea and
• Calin Deleanu

Beilstein J. Org. Chem. 2017, 13, 659–664, doi:10.3762/bjoc.13.65

• isoxazole derivative, namely 3,5-difluorophenyl-[3-methyl-4-(methylsulfonyl)isoxazol-5-yl]methanone, was recently reported as an inducer of nitric oxide producing elicitor in plants [16][17]. Nitric oxide (NO), which has been demonstrated to be a major gasotransmitter in mammals, is also involved in the

• reactive oxygen species (ROS) production in plant tissues. Usually, NO and ROS, such as O2−, OH· and H2O2, together are required to induce the activation of various defense-related enzymes in plants [55]. Plant cells contain oxygen radical detoxifying enzymes and nonenzymatic antioxidants which have an

• generation in plant tissues and could activate various defense mechanisms in plants. Further research is in progress to assess the in planta mechanism of NO generation by these compounds. Synthetic route to 3,5-disubstituted isoxazoles. Reported 3,5-disubstituted isoxazoles. Supporting Information

Solid-phase enrichment and analysis of electrophilic natural products

• Frank Wesche,
• Yue He and
• Helge B. Bode

Beilstein J. Org. Chem. 2017, 13, 405–409, doi:10.3762/bjoc.13.43

• also be applied to extracts of other bacteria, fungi and plants and can give at least hints on new electrophilic natural products, where their reactivity against azide might also reflect their biological activity. (A) HPLC–MS base peak chromatograms of a crude XAD extract of P. luminescens TT01 and

Diels–Alder reactions of myrcene using intensified continuous-flow reactors

• Christian H. Hornung,
• Miguel Á. Álvarez-Diéguez,
• Thomas M. Kohl and
• John Tsanaktsidis

Beilstein J. Org. Chem. 2017, 13, 120–126, doi:10.3762/bjoc.13.15

• referred to in the following only as “myrcene” (1), see Scheme 1, vide infra). It can be found in significant quantities (up to 39%) in the essential oils of several plants, such as wild thyme [4], ylang-ylang [5], bay leaf [6], juniper berries [7], lemongrass [8], or parsley [9], and in smaller

First DMAP-mediated direct conversion of Morita–Baylis–Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates

• Marwa Ayadi,
• Haitham Elleuch,
• Emmanuel Vrancken and
• Farhat Rezgui

Beilstein J. Org. Chem. 2016, 12, 2906–2915, doi:10.3762/bjoc.12.290

• biological potentials. Aminophosphonates and their derivatives [22][23][24][25][26] are thus recognized as promising compounds and a new class of drugs that are widely used in a variety of commercial applications. Indeed, they are known to influence various biochemical processes in plants, modifying or

O-Alkylated heavy atom carbohydrate probes for protein X-ray crystallography: Studies towards the synthesis of methyl 2-O-methyl-L-selenofucopyranoside

• Roman Sommer,
• Dirk Hauck,
• Annabelle Varrot,
• Anne Imberty,
• Markus Künzler and
• Alexander Titz

Beilstein J. Org. Chem. 2016, 12, 2828–2833, doi:10.3762/bjoc.12.282

• -methylated carbohydrate ligands was demonstrated (e.g., 2, Figure 1). O-Methylation of carbohydrates is a rare modification, but widespread in nature as it has been observed in bacteria, protozoa, animals and plants but not in mammals [29][30]. Besides fungal and animal tectonins that recognize O-methylated

Interactions between cyclodextrins and cellular components: Towards greener medical applications?

• Loïc Leclercq

Beilstein J. Org. Chem. 2016, 12, 2644–2662, doi:10.3762/bjoc.12.261

• are, with proteins and lipids, essential constituents of living organisms because they are key biological intermediates for energy storage. In autotrophs, such as plants, sugars are converted into starch whereas for heterotrophic organisms, such as animals, they are stored as glycogen. However

• , polysaccharides serve also as structural components: cellulose for plants and chitin for arthropods. Moreover, saccharides and their derivatives play key roles in the immune system, fertilization, blood clotting, information transfer, etc. For instance, the 5-carbon monosaccharide ribose forms the backbone of the

A detailed view on 1,8-cineol biosynthesis by Streptomyces clavuligerus

• Jan Rinkel,
• Patrick Rabe,
• Laura zur Horst and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2016, 12, 2317–2324, doi:10.3762/bjoc.12.225

• complexity is reached within the largest, the terpenoids. An estimated number of 75,000 different compounds are known from all kinds of organisms including plants [1], bacteria [2][3][4][5], fungi [6] and, as recently shown, even social amoebae [7]. These molecules are all made from only a handful of linear

• conserved motifs including the aspartate-rich motif (DDXXD) and the NSE triad (ND(L,I,V)XSXXXE, modified in plants to a DTE triad: DD(L,I,V)XTXXXE) [8]. Their substrates bind with the diphosphate portion to the (Mg2+)3 cluster and via hydrogen bridges to a highly conserved arginine (diphosphate sensor) and