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Natural products have been a source of inspiration for chemists and chemical biologists for many years, and have a special relevance in the chemical space. In recent years, several novel synthetic strategies have appeared, such as diversity-oriented synthesis (DOS), biological-oriented synthesis (BiOS), and function-oriented synthesis (FOS), for accessing complex and functionally diverse molecules. In this manner, the synthesis of natural products has evolved towards simpler and ecological methods using biotransformation, combinatorial chemistry, or organocatalysts. In this issue, Prof. Chojnacka shows demonstrates the use of immobilized lipases as catalysts to aid in the synthesis of phosphatidylcholine enriched with myristic acid. Profs. Vila and Pedro used catalysts derived from (S)-mandelic acid to achieve the catalytic enantioselective addition of dimethylzinc to isatins. Prof. Diez shows the possibility of the obtention of 7,8-carvone epoxides in a diastereoselective manner using proline, quinidine, and diphenylprolinol as organocatalysts. A cheap, simple, clean, and scalable method involves the use of deep eutectic mixtures as reaction media, and Profs. Alonso and Guillena describe the use of this methodology for the enantioselective, organocatalyzed ?-amination of 1,3-dicarbonyl compounds. Biotransformations have been one of the methodologies for more efficient synthesis of natural products. Prof. Wu transforms ergostane triterpenoid antcin K using Psychrobacillus sp. Ak 187. Finally, Prof. Kovayashi reviews the total synthesis and biological evaluation of phaeosphaerides. The reader, through this issue, could gain an idea of the new directions that the synthesis of natural products using catalysts will have in the years to come.

n/a --- structured phosphatidylcholine --- carvone --- immobilized lipases --- trimyristin --- 3-hydroxyoxindole --- green chemistry --- structural revision --- anticancer --- triterpenoid --- organocatalysis --- natural products --- epoxidation --- ?-amination --- benzimidazole --- total synthesis --- zinc --- Antrodia cinnamomea --- aminocatalysis --- epoxide --- asymmetric organocatalysis --- mandelamides --- STAT3 --- asymmetric catalysis --- Psychrobacillus --- isatin --- chiral ?-hydroxyamide --- interesterification --- proline --- phaeosphaeride B --- biotransformation --- phaeosphaeride A --- myristic acid --- egg-yolk phosphatidylcholine --- acidolysis --- antcin K --- deep eutectic solvents

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Layered double hydroxides (LDHs), also known as two-dimensional anionic clays, as well as the derived materials, including hybrids, nanocomposites, mixed oxides, and supported metals, have been highlighted as outstanding heterogeneous catalysts with unlimited applications in various processes involving both acid–base (addition, alkylation, acylation, decarboxylation, etc.) and redox (oxidation, reduction, dehydrogenation, etc.) mechanisms. This is mainly due to their flexibility in chemical composition, allowing the fine tuning of the nature of the active sites and the control of the balance between them. Additionally, LDHs display a large anion exchange capacity and the possibility to modify their interlayer space, constraining the size and type of reactants entering in the interlamellar space. Furthermore, their easy and economic synthesis, with high levels of purity and efficiency, at both the laboratory and industrial scales, make LDHs and their derived materials excellent solid catalysts. This Special Issue collects original research papers, reviews, and commentaries focused on the catalytic applications of these remarkable materials.

layered double hydroxides (LDH) --- polyoxometalates (POM) --- catalytic materials --- Michael addition --- cobalt-based LDHs --- ultrasonic irradiation --- synergistic effect --- photocatalysis --- nitrophenol degradation --- Zn,Al-hydrotalcite --- ZnO dispersed on alumina --- reusability --- layered double hydroxide --- LDH --- catalytic oxidation --- ethanol --- toluene --- VOC --- photocatalysts --- Cu electrodes --- diazo dyes --- electrocatalysts --- layer double hydroxides --- photoelectrochemical degradation --- hydrotalcites --- mixed oxides --- aldol condensation --- basic catalysts --- exfoliation --- nanosheets --- oxidation --- layered double hydroxides --- base catalysts --- epoxide --- formaldehyde --- oxidation removal --- BiOCl --- manganese --- biodiesel --- transesterification --- hydrothermal --- nickel --- aluminum --- solid base --- structured catalyst --- ethanol steam reforming --- aluminum lathe waste strips --- Ni nanoparticle --- mechano-chemical/co-precipitation synthesis --- organic alkalis (tetramethylammonium hydroxide) --- memory effect --- Claisen-Schmidt condensation --- self-cyclohexanone condensation --- n/a

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BioPolymers could be either natural polymers – polymer naturally occurring in Nature, such as cellulose or starch…, or biobased polymers that are artificially synthesized from natural resources. Since the late 1990s, the polymer industry has faced two serious problems: global warming and anticipation of limitation to the access to fossil resources. One solution consists in the use of sustainable resources instead of fossil-based resources. Hence, biomass feedstocks are a promising resource and biopolymers are one of the most dynamic polymer area. Additionally, biodegradability is a special functionality conferred to a material, bio-based or not. Very recently, facing the awareness of the volumes of plastic wastes, biodegradable polymers are gaining increasing attention from the market and industrial community. This special issue of Molecules deals with the current scientific and industrial challenges of Natural and Biobased Polymers, through the access of new biobased monomers, improved thermo-mechanical properties, and by substitution of harmful substances. This themed issue can be considered as collection of highlights within the field of Natural Polymers and Biobased Polymers which clearly demonstrate the increased interest in this field. We hope that this will inspire researchers to further develop this area and thus contribute to futures more sustainable society.”

imine --- epoxide --- amine --- thermoset --- bio-based --- biobased epoxy --- cardanol --- cationic photocuring --- microfibrillated cellulose --- biobased composites --- sustainable materials --- biomass --- green chemistry --- mechanims --- humins --- epoxy resins --- thermosets --- kinetics --- ring-opening --- biobased --- polyurethane foam --- catalyst --- polycarbonates --- furan-maleimide --- Diels-Alder --- fatty acids --- melt extrusion --- 3D printing --- cellulose nanofibrils --- biocomposite filaments --- physical property --- drained and undrained peatlands --- peats --- humic acids --- thermal --- paramagnetic and optical properties --- acetylated starch --- etherified starch --- chemical composition --- macromolecular characteristics --- surface characterization --- lignin --- fractionation --- biobased polymers --- solvent extraction --- membrane-assisted ultrafiltration --- plant oil-based monomers --- mixed micelles --- methyl-β-cyclodextrin inclusion complex --- emulsion polymerization --- nanocellulose --- polymer --- coating --- textile --- adhesion --- biobased monomer --- photoinduced-polymerization --- eugenol-derived methacrylate --- bacterial cellulose --- alginate --- gelatin --- curcumin --- biomaterials --- chitosan --- silane coupling agent --- microfiber --- crosslinking --- mechanical strength --- block copolymers --- renewable resources --- RAFT --- alkyl lactate --- PSA --- terpenoid --- exo-methylene --- conjugated diene --- renewable monomer --- biobased polymer --- radical polymerization --- copolymerization --- living radical polymerization --- RAFT polymerization --- heat-resistant polymer --- n/a

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The Special Issue “Molecules from Side Reactions” is a collection of papers reporting on the synthesis and characterization of the molecules that come from unexpected synthetic routes. This is the first example of a Special Issue based on such a topic, notwithstanding that all synthetic chemists have isolated a side product during a chemical reaction. Instead of continuing to store the side products in the freezer, I have thought to give them the dignity of publication, making them available to the scientific community. The short manuscripts collected here respect the principle of “one compound per paper” and have the purpose of preserving the molecular diversity deriving from a chemical reaction. The molecular scaffolds are unexpected and intriguing, and could be useful starting points or intermediates for exploring novel reactions.

oxazole --- furan --- RORC reaction --- (E,Z)-isomerization --- nitration --- azaheterocycles --- N–C bond cleavage --- pyridine-imidazolium --- ribose --- psicose --- ketose --- rare sugar --- hydroxy methylation --- AICAR --- acadesine --- phosphorylation --- fluorination --- fluorinated nucleosides --- nucleoside analogues --- modified nucleosides --- chlorinated nucleosides --- AMPK --- organic synthesis --- bidentate directing groups --- benzamides --- chelation assistance --- bis-chelates --- C–H bond functionalization --- X-ray structure determination --- N′-acetylhydrazide --- 3-acetyl-2,3-dihydro-1,3,4-oxadiazole --- 1H-pyrazolo[3,4-b]pyridine --- heterocycle --- oxetane --- epoxide --- rearrangement --- carbohydrate --- C-glycosylation --- spiro-oxetane --- ester group migration --- glycosyl sulfoxide --- uronate --- thioglycoside oxidation --- mannose --- 8-Fluoro-2′-deoxyguanosine --- 19F NMR spectroscopy --- solid phase synthesis --- phosphoramidite --- muraymycins --- caprazamycins --- nucleosides --- uridine --- cyclization --- seven-membered rings --- conjugated diyne --- LAH reduction --- diacetal --- pent-1,2,3,4-tetraene intermediate --- ligand --- pyridine derivatives --- allenic compounds --- N-alkylation --- copper --- cyanide --- network --- guanidinium --- unexpected iminium cation --- n/a --- N-C bond cleavage --- C-H bond functionalization --- N'-acetylhydrazide --- 8-Fluoro-2'-deoxyguanosine

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Homogeneous catalysis owes its success, in large part, to the development of a wide range of ligands with well-defined electronic and steric properties, which have thus made it possible to adjust the behavior of many organometallic complexes. However, ligands used in catalysis have long been centered on elements of group 15, and it is only more recently that carbon ligands have proved to be valuable alternatives with the emergence of cyclic diaminocarbenes (NHC).This Special Issue aims to provide a contemporary overview of the advances in carbon ligand chemistry from fundamental aspects to applications.

carbenes --- ylides --- DFT calculations --- electronic structure --- catalysis --- ligands --- structure–activity relationship --- NHC --- nanoparticle --- calixarene --- palladium catalyst --- Suzuki-Miyaura reaction --- amino-acids --- water --- carbon ligand --- amide --- negative charge --- phosphonium ylide --- oxide --- pincer --- metathesis --- ruthenium --- nitro catalysts --- NHC ligands --- olefins --- selenonium ylides --- selenonium salts --- chirality --- stereogenic selenium atom --- asymmetric synthesis --- optical resolution --- reactivity --- malaria --- Plasmodium falciparum --- gold --- NHC-ligands --- hybrid molecules --- drug resistance --- N-heterocyclic carbene --- platinum --- metal complexes --- 195Pt NMR --- N-heterocyclic carbenes --- imidazole --- spectroscopy --- X-ray --- mercury(II) complex --- T-shaped --- carbodiphosphorane --- phosphorus ylides --- pincer ligands --- coordination chemistry --- Cu(I) complex --- photoluminescence --- titanium --- hafnium --- copolymerization of epoxide with CO2 --- density functional theory --- natural bond orbitals --- aromaticity --- ion pairs --- alkali metals --- tropylidenyl ions --- cyclooctatetraene ions --- rhodium --- electron paramagnetic resonance (EPR) spectroscopy --- density functional theory (DFT) --- electrochemistry --- carbone complexes --- carbido complexes --- transition metal complexes --- chemical bonding --- pincer ligand --- macrocycle --- lithium --- potassium --- intramolecular C-H activation --- dehydrogenation --- carbone --- ligand --- germylene --- coordination --- ylide --- n/a --- structure-activity relationship