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The Pd-catalyzed inter- and intramolecular reactions of nitrogen compounds are often carried out with palladium carboxylates, sometimes in the presence of carboxylic acids or alkali metal carboxylates. This Mini-Review highlights the dependence of the reaction efficiency on the nature of the ligand and the carboxylate additives. The proposed reaction mechanisms are presented with, as far as possible, personal comments.

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A rich array of reactions occur using N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc) as reactants, these two amides being able to deliver their own H, C, N, and O atoms for the synthesis of a variety of compounds. This account highlights the literature published since June 2018, completing previous reviews by the author.

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In a novel approach, an efficient non-enzymatic glucose sensor based on pure phase of aurivillius bismuth molybdate (BM or γ-Bi2MoO6) mixed metal oxides is reported. Three BM samples were synthesized, with/without l-cysteine (Cys) and dodecylamine (DDA) as additives, leading to different shapes: bullet (BM-C), confetti (BM-2Cys) and candy (BM-2DDA). The morphology and purity of the structures were confirmed by FE-SEM images and XRD. In order to investigate the sensor application, the samples were integrated on reduced graphene oxide and incorporated into simple and inexpensive glassy carbon electrode (GCE) without using any polyvinylpyrrolidone (PVP) or Nafion. To perform cyclic voltammetry experiments, all three biosensors were measured in PBS solution (pH = 7) in ±1.5 voltage range and 50 mV s-1 scan rate. Glucose identification by the synthesized composites is an obvious sign of their high efficiency. According to chronoamperomograms, the best sensitivity of 3050 µA L mmol-1 cm-2 with linear range of 0.02-0.14 mmol L-1, low detection limit (LOD) of 0.004 mmol L-1 and the signal/noise equal to 3 was achieved by BM-2DDA/rGO/GCE biosensor and its speedy amperometric response is less than 5 s. This biosensor showed impressive selectivity, repeatability and reproducibility results besides it maintains its stability considerably in great percentage of 98.5% after eight weeks. Also it showed prolonged stability after 50 min.

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The oxygenation of cyclohexane and toluene by O2 and H2O2 catalyzed by VO(acac)2 and Co(acac)2 was studied at 40-100 °C and 1-10 atm. Upon such conditions, the process can be remarkably (30× times) enhanced by the minute (6-15 mM) additives of oxalic acid (OxalH) or N-hydroxyphthalimide (NHPI). The revealed effect of OxalH on H2O2-piloted oxidation is closely associated with the nature of the catalyst cation and boosted by VO(acac)2. Whereas the effectiveness of Co(acac)2-based systems was curbed by the addition of OxalH and remained much below the one displayed with the previous system. The observed conspicuous difference in activity was attributed to the substantially higher solubility of in situ formed VO(IV)oxalate compared to that of Co(II)oxalate. The exploration of H2O2 for the NHPI-promoted process leads to the decisively lower (5-7 times) yield in comparison to the O2-driven reaction. Similarly, for the O2-operated protocol, the yield cannot be improved by addition of OxalH either to VO(acac)2 + NHPI or to Co(acac)2 + NHPI mixture. By contrast, the combination of NHPI with VO(acac)2 or Co(acac)2 and particularly with the above two mixtures in O2-piloted oxidation enhances the yield of the aimed products 3-6 times regardless of the substrate used. The revealed significant synergetic effect of the cobalt + vanadyl bicomponent catalyst was due to the participation of each of its moiety in the different stages of the process mechanism. Only benzyl alcohol and benzaldehyde were identified in VO(acac)2- or Co(acac)2-catalyzed toluene oxidation, while cyclohexane oxidation yields cyclohexylhydroperoxide in line with cyclohexanol and cyclohexanone. The putative mechanism of investigated processes is highlighted and discussed.

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N,N-Dimethylformamide and N,N-dimethylacetamide are multipurpose reagents which deliver their own H, C, N and O atoms for the synthesis of a variety of compounds under a number of different experimental conditions. The review mainly highlights the corresponding literature published over the last years.

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A new derivative of dipodal 1,3-calix[4]arene-based chemosensor (R), which was containing several binding sites have been synthesized and characterized by NMR, IR and LC-MS spectroscopic methods. The selectivity of Rhas been investigated in aqueous methanol, resulting in fluorescence shift and selective recognition of Ag+ among 20 various alkali, alkaline earth and transition metal ions. Microstructural features of R and its complex with Ag+have been investigated by Atomic Force Microscopy (AFM). AFM images can clearly differentiate R from its complex of Ag+. Moreover; the complicated binding mode of metal-ligand complex has been explored by UV-Vis, LC-MS, FIR, Fluorescence titration, Job's plot method and theoretical approaches. Density functional theory (DFT) method at B3LYP/LANL2DZ level of theory was employed for computational studies. Theoretical calculations revealed that selectivity and specificity of R toward Ag+ could be attributed to structural conformation of 1,3-alternate-calix[4]arene scaffold and molecular electrostatic potential of its surface. Furthermore; the competitive experiments were carried out to test sensor's ability for practical uses. Finally, the efficiency of R in matrix of physiological cations was examined and showed gradual emission enhancement which makes R an ideal candidate for monitoring of Ag+ in physiological environment.

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In a new approach, shape controlled synthesis of zinc oxide nanostructures were carried out using a solvothermal route assisted amino acids such as L-Lysine (lysine), L-Cysteine (cysteine) and L-Arginine (arginine) as bifunctional species with (or without) urea or oxalic acid as additives which affect the pH of the reaction. Rod, powder, particle, cube, rock candy-like, sheet, sphere, brain-like, groundnut-like and pussy willow-like morphologies were obtained through the synthetic route. Particle sizes varied from 25 nm to4 µm. To test the application, nine ZnO nanostructures, formulated by multi-walled carbon nanotube (MWCNT) on glassy carbon electrode (GCE) were applied as new nanobiosensors for detecting glucose in a simple and inexpensive way without using any glucose oxidase or nafion. Glucose sensing accomplished in a phosphate buffer solution (PBS, pH=7) for ZnO/MWCNT/GCE samples. Results showed that in this non-enzymatic biosensor system, spherical ZnO obtained from zinc acetate/cycteine/oxalic acid synthetic route has the highest sensitivity of 64.29 µA/cm(2) mM with repeatable results. For the mentioned sensor, no interference observed in the presence of dopamine, uric acid and fructose.

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The Pd-catalysed formation of a C-O bond from allenes mainly occurs via the inter- or intramolecular reaction with a hydroxyl group belonging to an alcohol, a phenol or an acid. A carbonyl or a carbonate entity can also be involved. In most cases, the formation of the C-O bond is one step of a domino reaction leading also to a C-C or C-N bond, or to another C-O bond. Thus, a wide range of products, in particular highly functionalized heterocycles, have been synthesised. Catalytic cycles have been proposed but the mechanisms often remain speculative.

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Nanocrystalline starch produced from the acid hydrolysis of gelatinized starch has been used for the first time to support palladium(II) ethylenediamine complex. The nanocrystalline starch supported Pd(II) complex was found to be an efficient and efficiently recycled catalyst for the Mizoroki-Heck reaction of furans and thiophenes with styrenes under mild reaction conditions.

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Electrospray ionization mass spectrometry, subsequent MS/MS, and high-resolution mass spectrometry were used to study the dehydrogenative Heck reaction of 2-alkylfurans 1 with acrylates 2, using [Pd(OAc)(2)](3) as the precatalyst, benzoquinone (BQ) as the stoichiometric oxidant, and a mixture of DMSO and AcOH as the solvent. Complexation of [Pd(OAc)(2)](3) by DMSO afforded mononuclear and dinuclear Pd(II) species, which proved to be active catalysts for the C-H activation of 1. Mononuclear and dinuclear Pd(II) species seem also to be involved in the insertion of 2 into the furyl-Pd bond. The C-H activation of 2 and DMSO by mononuclear complexes was observed. The reaction leads to 5,5'-dialkyl-2,2'-bifuran 4 as a byproduct. Bifuryl-palladium, which is an intermediate in the formation of 4, showing the coordination of BQ, was obtained and characterized.

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The oxidation of starch, xylans, potato flesh and wheat flour by H(2)O(2), in the presence of MSO(4) (M=Cu, Fe) as catalyst, led to depolymerization, and formation of solutions containing polyhydroxycarboxylic acids. Some of these oxidized compounds facilitate the process, leading to efficient transformations even with very low amounts of catalyst.

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The efficiency and the selectivity of the Pd-catalyzed oxidation, in carboxylic acids, of terminal alkenes are strongly improved in the presence of a base. The methodology is particularly well adapted for the oxidation of homoallylic alcohols, for which the resulting acyloxylated products are obtained selectively as E-isomers in fair to good yields.

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The telomerization of butadiene with alcohols is an elegant way to synthesize ethers with minimal environmental impact since this reaction is 100% atom efficient. Besides telomerization of butadiene with methanol and water that is industrially developed, the modification of polyols is still under development. Recently, a series of new substrates has been involved in this reaction, including diols, pure or crude glycerol, protected or unprotected monosaccharides, as well as polysaccharides. This opens up the formation of new products having specific physicochemical properties. We will describe recent advances in this field, focusing on the reaction of renewable products and more specifically on saccharides. The efficient catalytic systems as well as the optimized reaction conditions will be described and some physicochemical properties of the products will be reported.

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Under palladium(II)-catalyzed and oxidative conditions, the coupling of furans with styrenes leads to the formation of Heck-type products in medium to good yields. The reaction is highly regio- and stereoselective, giving trans-olefins predominantly.

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A series of large glycodendrimers containing 27, 81, and 243 terminal modified xylose branches from the first (G(1)-27) to the third generation (G(3)-243) were synthesized from 2'-azidoethyl 2,3,4-tri-O-acetyl-beta-d-xylopyranoside and alkynyl-terminated dendrimers by "click" chemistry that is confirmed to be an excellent method to obtain large glycodendrimers exemplified by the use of modified xylose. The dendrimers were first characterized by (1)H NMR, (13)C{(1)H} NMR, elemental analysis, and IR spectroscopy. The size progression in the series was also demonstrated using both DOSY NMR and size exclusion chromatography (SEC), the latter technique showing the good polydispersity of all the dendrimers. The size measured by dynamic light scattering (DLS) for the dendrimer G(3)-243 is close to that obtained by the DOSY NMR method.

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An efficient method for the preparation of various substituted 2-mercapto benzimidazoles from their corresponding thioureas has been developed. S-alkylation of thioureas followed by Cu-catalyzed intramolecular N-arylation furnished substituted 2-mercapto benzimidazoles in high yields and short reaction times. Furthermore, 2-mercapto benzimidazoles substituted with a p-methoxybenzyl group allowed access to benzimidazole thiones.

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The Pd(OCOCF3)2/[(HOCH2CH2NHCOCH2)2NCH2]2-catalyzed oxidation of o-allylphenol with H2O2 in water/methanol affords a syn and anti mixture of 2-(1,2-dihydroxypropyl)phenol and 2-(2-hydroxy-1-methoxypropyl)phenol. Mechanistic experiments and ESI-MS studies support a pathway wherein isomerization of the C=C bond followed by its epoxidation and oxirane opening led to the products. Recycling of the catalytic system led to gradual lost of activity.

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Unsaturated fatty alkyl xylosides and the corresponding 1-O-acyl esters were prepared. Critical micellar concentrations, surface tension areas per molecule and foaming value of some of these new amphiphilic compounds have been determined.

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