Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids

• László Orha,
• József M. Tukacs,
• László Kollár and
• László T. Mika

Beilstein J. Org. Chem. 2019, 15, 2907–2913, doi:10.3762/bjoc.15.284

• excellent yields (72–99%) and purity (>98%). These results represent an example which proves that biomass-derived safer solvents can be utilized efficiently in common, industrially important transformations exhibiting higher chemical and environmental efficiency. Keywords: catalysis; cross coupling; green

• been carried out in γ-valerolactone-originated ILs, which can act as solvent, ligand and base. Thus, the preparation of various acetylenes in a partially or even biomass-based solvent without any auxiliary material could further control and reduce the environmental impacts of this industrially

Fluorine-containing substituents: metabolism of the α,α-difluoroethyl thioether motif

• Andrea Rodil,
• Alexandra M. Z. Slawin,
• Nawaf Al-Maharik,
• Ren Tomita and
• David O’Hagan

Beilstein J. Org. Chem. 2019, 15, 1441–1447, doi:10.3762/bjoc.15.144

• . After 72 h, the fungal biomass was removed and washed with diethyl ether. The supernatant was extracted into diethyl ether (3 × 50 mL) and dichloromethane (3 × 50 mL), and the combined organic extracts were dried over anhydrous Na2SO4, filtered and evaporated under reduced pressure. The extracts were

Mechanochemical amorphization of chitin: impact of apparatus material on performance and contamination

• Thomas Di Nardo and
• Audrey Moores

Beilstein J. Org. Chem. 2019, 15, 1217–1225, doi:10.3762/bjoc.15.119

• : amorphization; biomass; chitin; hardness; mechanochemistry; metal contamination; Introduction The last decade has seen a tremendous development in the field of mechanochemistry, which was notably covered in the New York Times in 2016 [1]. Yet, mechanochemistry is hardly a novel concept, since it is likely

• materials, which are distinct from what is enabled via solvothermal methods [6][7][8]. Finally, it also opens novel opportunities to react and functionalize solvent recalcitrant materials [9][10][11][12][13], including biomass-based materials [14][15][16][17][18][19][20][21][22][23][24][25]. Although the

• doping effects in coordination polymers [40][41]. Yet a systematic study of quantitative contamination as a function of the medium has not been reported. Mechanochemistry is a promising strategy towards the activation, functionalization and deconstruction of biomass. Mechanochemical activation can

Ugi reaction-derived prolyl peptide catalysts grafted on the renewable polymer polyfurfuryl alcohol for applications in heterogeneous enamine catalysis

• Alexander F. de la Torre,
• Gabriel S. Scatena,
• Oscar Valdés,
• Daniel G. Rivera and
• Márcio W. Paixão

Beilstein J. Org. Chem. 2019, 15, 1210–1216, doi:10.3762/bjoc.15.118

• ) – derived from a renewable resource like sugar cane biomass – for the incorporation of chiral pyrrolidine-based motifs capable to catalyze relevant asymmetric reactions. The incorporation of an organocatalyst into a polymer support requires either conjugation to the polymer or functionalization with a

New terpenoids from the fermentation broth of the edible mushroom Cyclocybe aegerita

• Frank Surup,
• Florian Hennicke,
• Nadine Sella,
• Maria Stroot,
• Steffen Bernecker,
• Sebastian Pfütze,
• Marc Stadler and
• Martin Rühl

Beilstein J. Org. Chem. 2019, 15, 1000–1007, doi:10.3762/bjoc.15.98

• . The biomass and suspended substrates was separated by centrifugation. RNA extraction, cDNA synthesis and qPCR During fermentation, mycelial samples were taken at day 2, 4, 7, 9, 11 and 14 and stored in RNAlater (Qiagen, Venlo, Netherlands) until further use. Fungal mycelium was freeze-dried and ground

Synthesis of a novel category of pseudo-peptides using an Ugi three-component reaction of levulinic acid as bifunctional substrate, amines, and amino acid-based isocyanides

• Maryam Khalesi,
• Azim Ziyaei Halimehjani and
• Jürgen Martens

Beilstein J. Org. Chem. 2019, 15, 852–857, doi:10.3762/bjoc.15.82

• by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials [18]. It can be used as a bifunctional precursor for the synthesis of pharmaceuticals, plasticizers, and different additives [19]. Furthermore, it is recognized as an excellent starting material

Ruthenium-based olefin metathesis catalysts with monodentate unsymmetrical NHC ligands

• Veronica Paradiso,
• Chiara Costabile and
• Fabia Grisi

Beilstein J. Org. Chem. 2018, 14, 3122–3149, doi:10.3762/bjoc.14.292

• the selective metathesis of linear α-olefins and was successfully applied to selectively re-equilibrate the naphtha fraction (C5–C8) of a Fischer–Tropsch feed derived from biomass to higher value added olefins (C9–C14) that can serve as plasticizer and detergent precursors. An excellent olefin

Thermophilic phosphoribosyltransferases Thermus thermophilus HB27 in nucleotide synthesis

• Ilja V. Fateev,
• Ekaterina V. Sinitsina,
• Aiguzel U. Bikanasova,
• Maria A. Kostromina,
• Elena S. Tuzova,
• Larisa V. Esipova,
• Tatiana I. Muravyova,
• Alexei L. Kayushin,
• Irina D. Konstantinova and
• Roman S. Esipov

Beilstein J. Org. Chem. 2018, 14, 3098–3105, doi:10.3762/bjoc.14.289

• 8.0. Fractions, containing the target enzyme with a purity of more than 96 %, were pooled and concentrated up to a concentration of 13 ± 1 mg/mL. Isolation and purification of TthAPRT: Cell biomass disruption and heat-treatment was performed as described in section "Isolation and purification of

Targeting the Pseudomonas quinolone signal quorum sensing system for the discovery of novel anti-infective pathoblockers

• Christian Schütz and
• Martin Empting

Beilstein J. Org. Chem. 2018, 14, 2627–2645, doi:10.3762/bjoc.14.241

• potent QSI compounds effectively suppressing AQ levels and 2-AA production at reasonable concentrations [69]. Lately, Maura and Rahme were able to demonstrate the effect of M64 (42) on biofilm formation [78]. Biofilm biomass was drastically reduced when treated with 1 and 10 µM of 42 compared to the

Impact of Pseudomonas aeruginosa quorum sensing signaling molecules on adhesion and inflammatory markers in endothelial cells

• Carmen Curutiu,
• Florin Iordache,
• Veronica Lazar,
• Aurelia Magdalena Pisoschi,
• Aneta Pop,
• Mariana Carmen Chifiriuc and
• Alina Maria Hoban

Beilstein J. Org. Chem. 2018, 14, 2580–2588, doi:10.3762/bjoc.14.235

• minutes, washed with distilled water and resuspended in a 33% acetic acid solution. The intensity of the suspension was spectrophotometrically assessed, the amount of adhered biomass being proportional to the absorbance value read at 492 nm. Adherence assay to cellular substrate Cell culture. Endothelial

Cobalt–metalloid alloys for electrochemical oxidation of 5-hydroxymethylfurfural as an alternative anode reaction in lieu of oxygen evolution during water splitting

• Jonas Weidner,
• Stefan Barwe,
• Kirill Sliozberg,
• Stefan Piontek,
• Justus Masa,
• Ulf-Peter Apfel and
• Wolfgang Schuhmann

Beilstein J. Org. Chem. 2018, 14, 1436–1445, doi:10.3762/bjoc.14.121

• large scale electrochemical hydrogen production. Advantageously, the oxidation of an alternative substrate at the anode, for example a biomass-derived fuel, allows to generate high value products besides hydrogen concomitantly with an increase in energy conversion efficiency during electrolysis [4

• valuable product is an appealing approach for increasing the competitiveness of the electrochemical hydrogen production. 5-Hydroxymethylfurfural (HMF) is a biomass-derived compound that can be converted to economically more valuable 2,5-furandicarboxylic acid (FDCA) via electrochemical oxidation at a

Spectroelectrochemical studies on the effect of cations in the alkaline glycerol oxidation reaction over carbon nanotube-supported Pd nanoparticles

• Dennis Hiltrop,
• Steffen Cychy,
• Karina Elumeeva,
• Wolfgang Schuhmann and
• Martin Muhler

Beilstein J. Org. Chem. 2018, 14, 1428–1435, doi:10.3762/bjoc.14.120

• oxidation. Keywords: cation effect; electrocatalysis; glycerol oxidation; in situ electrochemistry/IR spectroscopy; Introduction The conversion of biomass to biofuels is a promising process for carbon-neutral energy conversion [1]. First-generation biofuels such as bioethanol or biodiesel are produced

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

• -sterilized aqueous solutions (0.05 M) at the time of inoculation. The fermentation was conducted at 30 °C for 7 days. After centrifugation and removal of the biomass, the supernatant was treated with 10% (w/v) XAD-2 resin (Sigma-Aldrich) in order to adsorb the secreted metabolites. The resin was thoroughly

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

• in both the oxidation and alkylation reaction reveals a potential method for the valorization of lignocellulosic biomass. Keywords: alkylation; benzyl alcohol; benzyl chloride; iron oxide; mechanochemistry; microwave-assisted oxidation; polysaccharide; toluene; Introduction Heterogeneous catalysis

• toluene, respectively) could find current application in the valorization of lignocellulosic biomass with heterogeneous catalysis. However, the use of heterogeneous catalysts in the aforementioned reactions usually requires a filtration or centrifugation step to recover the catalyst. In order to simplify

Selective enzymatic esterification of lignin model compounds in the ball mill

• Ulla Weißbach,
• Saumya Dabral,
• Laure Konnert,
• Carsten Bolm and
• José G. Hernández

Beilstein J. Org. Chem. 2017, 13, 1788–1795, doi:10.3762/bjoc.13.173

• “Tailor Made Fuels from Biomass” (TMFB), which are funded by the Excellence Initiative of the German federal and state governments. We are also grateful to the European Union (Marie Curie ITN ‘SuBiCat’ PITN-GA-2013-607044, S.D.) for financial support.

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

• , or cellulose microfibrils from biomass. For this process to be optimal, some fundamental aspects of the structural and ultrastructural characterization of the cellulosic material have to be ascertained. Indeed, the extraction process should be adapted to the specificity of the various sources (e.g

New tricks of well-known aminoazoles in isocyanide-based multicomponent reactions and antibacterial activity of the compounds synthesized

• Maryna V. Murlykina,
• Maryna N. Kornet,
• Sergey M. Desenko,
• Svetlana V. Shishkina,
• Oleg V. Shishkin,
• Aleksander A. Brazhko,
• Vladimir I. Musatov,
• Erik V. Van der Eycken and
• Valentin A. Chebanov

Beilstein J. Org. Chem. 2017, 13, 1050–1063, doi:10.3762/bjoc.13.104

• obtained were evaluated for their antibacterial activity and several of them demonstrated a weak antimicrobial effect, but for most of the compounds a 30–50% increase in biomass of Gram-positive strains (mainly B. subtilis) compared to control was observed. Keywords: 3-amino-5-methylisoxazole; 5-amino-N

• ., anticancer, antidiabetic, etc., because in this case a negative influence on a microflora of the organism is decreased [110]. The other interesting feature of most of the compounds was the 30–50% increase in biomass of Gram-positive strains (mainly B. subtilis) compared to control. As it follows from a brief

• while scaling up the production of biomass with the aim of shortening the time and saving resources [120][121]. Although this is a subject for a future detailed study the results of antibacterial activity allowed outlining the positive tendency. Conclusion In summary, the behavior of 5-amino-N-aryl-1H

Fluorescent carbon dots from mono- and polysaccharides: synthesis, properties and applications

• Stephen Hill and
• M. Carmen Galan

Beilstein J. Org. Chem. 2017, 13, 675–693, doi:10.3762/bjoc.13.67

• ., graphite or graphene. Conversely bottom-up methodologies rely on the use of a molecular precursor which can be treated in such a way as to seed the formation of a CD. Typical starting materials include amino acids, citric acid, biomass and carbohydrates to name but a few, which can be reacted using thermal

• oligosaccharides or monosaccharide units. Thus, it is unsurprising that these naturally occurring materials have also been used as CD precursors. Many CD syntheses report the use of biomass, particularly sourced from plant matter, which is essentially a huge source of naturally derived polysaccharides combined

Secondary metabolome and its defensive role in the aeolidoidean Phyllodesmium longicirrum, (Gastropoda, Heterobranchia, Nudibranchia)

• Alexander Bogdanov,
• Cora Hertzer,
• Stefan Kehraus,
• Samuel Nietzer,
• Sven Rohde,
• Peter J. Schupp,
• Heike Wägele and
• Gabriele M. König

Beilstein J. Org. Chem. 2017, 13, 502–519, doi:10.3762/bjoc.13.50

• with the MeOH extract (3 × 150 mL) of the slug biomass and the solvents were evaporated. After liquid–liquid separation of the methanolic crude extract (4.5 g) between 100 mL H2O and 3 × 100 mL ethyl acetate (EtOAc), EtOAc solubles (2.2 g) were fractionated by vacuum liquid chromatography (VLC) over

Revaluation of biomass-derived furfuryl alcohol derivatives for the synthesis of carbocyclic nucleoside phosphonate analogues

• Bemba Sidi Mohamed,
• Christian Périgaud and
• Christophe Mathé

Beilstein J. Org. Chem. 2017, 13, 251–256, doi:10.3762/bjoc.13.28

• compounds were evaluated for their activity against a large number of viruses. However, none of them showed significant antiviral activity or cytotoxicity. Keywords: analogue; antiviral; carbocyclic; nucleoside; phosphonate; Introduction Biomass is a valuable resource in search of renewable organic carbon

• catalytic hydrogenation of furfural; the latter is obtained from the dehydration of xylose, a 5-carbon sugar derived from vegetal biomass. Furfuryl alcohol finds widespread application in the chemical industries and for example is employed for the production of synthetic fibers, fine chemicals, etc. In fine

Green chemistry

• Luigi Vaccaro

Beilstein J. Org. Chem. 2016, 12, 2763–2765, doi:10.3762/bjoc.12.273

• recovery and reuse of the materials needed for a synthetic process. It is also very important to promote the use of biomass-derived chemicals that feature an intrinsically lower CO2 consumption. Additionally, the pivotal role of catalysis is indisputable. Significant efforts are being directed towards the

Diels–Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels–Alder reaction

• Ángel Cantín,
• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2016, 12, 2181–2188, doi:10.3762/bjoc.12.208

• selectivity and atom economy. Moreover, Diels–Alder cycloadditions in combination with heterogeneous catalysts (i.e. doped-microporous materials) represent an interesting approach for the conversion of biomass feedstock into stable chemicals such as furfural derivatives, platform molecules which can be

Silica-supported sulfonic acids as recyclable catalyst for esterification of levulinic acid with stoichiometric amounts of alcohols

• Raimondo Maggi,
• N. Raveendran Shiju,
• Veronica Santacroce,
• Giovanni Maestri,
• Franca Bigi and
• Gadi Rothenberg

Beilstein J. Org. Chem. 2016, 12, 2173–2180, doi:10.3762/bjoc.12.207

• Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands. Tel: +31-20-5256515 Istituto IMEM-CNR, Parco Area delle Scienze 37/A, I-43124 Parma, Italy 10.3762/bjoc.12.207 Abstract Converting biomass into value-added chemicals holds the key to sustainable long-term carbon resource management. In this

• : esterification; heterogeneous catalysis; renewable feedstocks; supported organic catalysts; sustainable chemistry; Introduction Vegetal biomass is mankind’s only source of renewable carbon on a human timescale. It is abundantly available, with the potential of replacing fossil-based carbon on a scale sufficient

• for covering the worldwide demand for non-fuel chemicals [1][2][3][4]. Currently, the main research thrust is directed at lignocellulose, the most abundant fraction of biomass. The mass composition of lignocellulose could be roughly represented by a 5/3/2 ratio of cellulose, hemicellulose and lignin

Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products

• Dmitry S. Ryabukhin,
• Dmitry N. Zakusilo,
• Mikhail O. Kompanets,
• Anton A.Tarakanov,
• Irina A. Boyarskaya,
• Tatiana O. Artamonova,
• Mikhail A. Khohodorkovskiy,
• Iosyp O. Opeida and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 2125–2135, doi:10.3762/bjoc.12.202

• 5-HMF and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibilities of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF. Keywords: 2,5-diformylfuran; Friedel–Crafts reaction; 5-hydroxymethylfurfural; superacids; zeolites

• molecules, such as alcohols, carboxylic acids, (hetero)aromatic ketones and aldehydes, phenols, etc. These biomass-derived platform chemicals are considered as an alternative and displacement to petroleum chemistry [17][18]. Among all these compounds, the preparation and reaction of 5-hydroxymethylfurfural

• production of new useful organic substances [26][27][28][29][30]. Based on our recent study on the synthesis of 5-HMF and its oxidation to 2,5-diformylfuran (2,5-DFF) [31] (Figure 1), this work is focused on developing methods of organic synthesis on the basis of electrophilic activation of these biomass

Experimental and theoretical insights in the alkene–arene intramolecular π-stacking interaction

• Valeria Corne,
• Ariel M. Sarotti,
• Carmen Ramirez de Arellano,
• Rolando A. Spanevello and
• Alejandra G. Suárez

Beilstein J. Org. Chem. 2016, 12, 1616–1623, doi:10.3762/bjoc.12.158

• , Universidad de Valencia, Valencia 46100, Spain 10.3762/bjoc.12.158 Abstract Chiral acrylic esters derived from biomass were developed as models to have a better insight in the aryl–vinyl π-stacking interactions. Quantum chemical calculations, NMR studies and experimental evidences demonstrated the presence

• affected by the electron density of the aromatic counterpart. Keywords: acrylic esters; asymmetric synthesis; biomass; conformational equilibrium; π-stacking interaction; Introduction Noncovalent interactions have demonstrated to have relevant importance in chemistry and biology [1][2][3][4]. Considering

• an element of stereocontrol in highly selective chemical transformations has been widely explored [9]. In this context, as part of our continuous interest in the development of new tools for asymmetric synthesis using levoglucosenone (a biomass-derived chiral enone) [10][11][12][13][14][15], we