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A systematic study is presented on the physical and photophysical properties of isoelectronic and isostructural Cu, Ag, and Au complexes with a common amide (N-carbazolyl) and two different carbene...

Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with a limited scope of substrates and/or reagents, with general solutions lacking. Herein, we describe a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes that is facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl- and aryl-substituted alkynes are coupled with a variety of boryl and silyl reagents with high α-selectivity. The reaction is scalable, and the products are versatile intermediates that can participate in various downstream transformations. Preliminary mechanistic experiments shed light on the role of CAAC ligands in this process.

Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with a limited scope of substrates and/or reagents, with general solutions lacking. Herein, we describe a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes that is facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl- and aryl-substituted alkynes are coupled with a variety of boryl and silyl reagents with high α-selectivity. The reaction is scalable, and the products are versatile intermediates that can participate in various downstream transformations. Preliminary mechanistic experiments shed light on the role of CAAC ligands in this process.

International audience; Discovered in 2005, cyclic (alkyl)(amino)carbenes (CAACs) have led to numerous discoveries in the field of ruthenium olefin metathesis, until then largely dominated by the well-known N-heterocyclic carbenes (NHCs). In comparison to the latter, CAACs are simultaneously more nucleophilic (σ-donating) and electrophilic (π-accepting), which leads to very strong metal-carbene bonds. Consequently, (CAAC)ruthenium complexes are very robust, which leads to enhanced catalytic activities, as exemplified by the industrially relevant ethenolysis of unsaturated fatty acids (TONs of up to 390000). Herein, we provide a comprehensive overview of the effect of CAAC ligands in olefin metathesis, including results which are described in patents.

In Sub-Saharan African countries, more than 60% of the active population is involved in agriculture. Synthetic pesticides and veterinary drugs are mainly imported from developed economies and are massively used and misused by the population. The level of environmental pollution by residues of these chemicals is considered to be a serious concern all over the continent. Populations and animals are at risk of exposure to highly polluted food and water. This chapter reviews the exposure levels to pesticides and veterinary drugs residues through selected highly consumed foods. Herbicides, insecticides and antibiotics are frequent residues found in foods; most foods items revealed contaminations by multiples chemicals. Levels of contamination are often higher than maximum residues limits set by the Codex Alimentarius or by the European Union. Preliminary estimations of consumers’ dietary exposure and health risk suggest a real public health concern from endocrine disrupting agrochemicals. Very few studies have been carried out so far on this concern and decision makers remain greatly unaware of the rising issue of health risks in Africa associated with exposure to hormonally active pesticides and veterinary drugs.

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An expedient access to the first optically pure ruthenium complexes containing

International audience; Many organic and main group compounds, usually acids or bases, can accelerate chemical reactions when used in substoichiometric quantities, a process known as organocatalysis. In marked contrast, very few of these compounds are able to activate carbon monoxide and, until now, none of them catalyze its chemical transformation, a classical task for transition metals. Herein, we report that a stable singlet ambiphilic carbene activates CO and catalytically promotes the carbonylation of an ortho-quinone into a cyclic carbonate. These findings pave the way for the discovery of metal-free catalyzed carbonylation reactions.

International audience; HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Although N-heterocyclic carbenes (NHCs) have been known as ligands for organometallic complexes since the 1960s, these carbenes did not attract considerable attention until Arduengo et al. reported the isolation of a metal-free imidazol-2-ylidene in 1991. In 2001 Crabtree et al. reported a few complexes featuring an NHC isomer, namely an imidazol-5-ylidene, also termed abnormal NHC (aNHCs). In 2009, it was shown that providing to protect the C-2 position of an imidazolium salt, the deprotonation occurred at the C-5 position, affording imidazol-5-ylidenes that could be isolated. Over the last ten years, stable aNHCs have been used for designing a range of catalysts employing Pd(II), Cu(I), Ni(II), Fe(0), Zn(II), Ag(I), and Au(I/III) metal based precursors. These catalysts were utilized for different organic transformations such as the Suzuki–Miyaura cross-coupling reaction, C–H bond activation, dehydrogenative coupling, Huisgen 1,3-dipolar cycloaddition (click reaction), hydroheteroarylation, hydrosilylation reaction and migratory insertion of carbenes. Main-group metal complexes were also synthesized, including K(I), Al(III), Zn(II), Sn(II), Ge(II), and Si(II/IV). Among them, K(I), Al(III), and Zn(II) complexes were used for the polymerization of caprolactone and rac-lactide at room temperature. In addition, based on the superior nucleophilicity of aNHCs, relative to that of their nNHCs isomers, they were used for small molecules activation, such as carbon dioxide (CO2), nitrous oxide (N2O), tetrahydrofuran (THF), tetrahydrothiophene and 9-borabicyclo[3.3.1]nonane (9BBN). aNHCs have also been shown to be efficient metal-free catalysts for ring opening polymerization of different cyclic esters at room temperature; they are among the most active metal-free catalysts for e-caprolactone polymerization. Recently, aNHCs successfully accomplished the metal-free catalytic formylation of amides using CO2 and the catalytic reduction of carbon dioxide, including atmospheric CO2, into methanol, under ambient conditions. Although other transition metal complexes featuring aNHCs as ligand have been prepared and used in catalysis, this review article summarize the results obtained with the isolated aNHCs.

International audience; Cyclic (alkyl)- and (aryl)-(amino)carbenes (CAACs and CAArCs) are stronger σ-donors and π-acceptors than imidazol-2-ylidenes and imidazolidin-2-ylidenes, the well-known N-heterocyclic carbenes (NHCs). Consequently, they form strong bonds with coinage metals and stabilize both low and high oxidation states. This Review shows that CAACs and CAArCs have allowed for the isolation of copper and gold complexes that were believed to be only transient intermediates. This has not only allowed for a better understanding of the mechanism of known processes but has also led to the development of novel coinage metal-catalyzed reactions. In addition to their role in homogeneous catalysis, CAAC and CAArC coinage metal complexes have recently found applications in medicinal chemistry, as well as in materials science. When possible, the performance of CAAC and CAArC ligands are compared with those of classical NHCs.

International audience; Cyclic (Alkyl)(Amino)Carbenes (CAACs) have become forceful ligands for gold due to their ability to form very strong ligandmetal bonds. Inspired by the success of Auranofin and other gold complexes as antitumor agents, we have studied the cytotoxicity of bis-and mono-CAAC-gold complexes on different cancer cell lines: HeLa (cervical cancer), A549 (lung cancer), HT1080 (fibrosarcoma) and Caov-3 (ovarian cancer). Further investigations aimed at elucidating their mechanism of action are described. This includes quantification of affinities for TrxR, evaluation of their bioavailability and determination of associated cell death process. Moreover, Transmission Electron Microscopy (TEM) was used to study morphological changes upon exposure. Noticeably, a significant reduction in non-specific binding to serum proteins was observed with CAAC complexes when compared to Auranofin. These results confirm the potential of CAAC-gold complexes in biological environments, which may result in more specific drug-target interactions and decreased side effects.

Aim and Objective: The development of small molecules that can interact with key therapeutic target represents an active field of research. Therefore, new approaches for increasing the molecular diversity of a starting material, such as a natural product, are needed. Herein, the carbonyl group present on a pregnane scaffold, or easily obtained from the oxidation of the corresponding alcohol, was used to obtain a series of diversified steroidal morpholinone derivatives. Materials and Methods: Using chemical synthesis, two levels of molecular diversity were introduced at position 20 of a C21-steroid scaffold. Nuclear magnetic resonance (NMR) spectroscopy and x-ray analysis were next used to characterize the morpholinone derivatives. Results: The C-20 carbonyl of pregnenolone was first transformed into an oxirane that reacted with an amino acid and the resulting amino alcohol was then cyclized to generate different spiro-2-morpholinones. X-ray analysis of one representative compound confirmed the 3-dimensional representation of this new family of diversified steroid derivatives. NMR analysis supported the expected structure and identified key markers of the chiral center configuration found in the 2-morpholinone moiety. Finally, the NH of the morpholinone ring was alkylated, thus increasing structural diversity. Conclusion: Considering the huge amount of building blocks (amino acids, bromobenzyl derivatives and ketones) that are commercially available, the strategy reported herein opens the door to the synthesis of diversified libraries of new compounds.

This paper investigates the dynamics of two models of jerk equations: The first one which is very simple and driven by an external constant signal, and the second one more complicated with an external periodic excitation. These particular equations are very important mathematical models of physical systems, with broad range applications in engineering, namely in electronic and telecommunication to generate the trains of regular and chaotic pulses. Although regular pulses are useful for the modulation of signals, the chaotic one can be used for the signal masking and modulations. The simplest jerk equation is chosen in the literature, while the periodic driven one is derived from Kirchhoff laws applied on a real electronic circuit conveniently built. The existence and uniqueness of their solutions are verified from the fixed- point theorem. Particularly by using the two parameters perturbation methods usually applied to find solitons, the periodic solutions are found, and proved to be sensitive to nonlinearity parameter and the external signal voltage’s amplitudes. The numerical investigations are next performed proving the existence of some interesting results such as the bubble bifurcation and the generation of chaotic pulses. Pspice and real experiments are performed on the periodic driven version of jerk equation in order to verify theoretical investigations.

Development of low-cost electrocatalyst for oxygen reduction reaction (ORR) is the main requirement for advanced chlor-alkali (ACA) cell. Herein, we report a simple and economical one-pot microwave assisted synthesis of nitrogen and phosphorus co-doped graphene (NPG) from graphene oxide in presence of ammonium dihydrogen phosphate. The optimized NPG showed well exfoliated graphene oxide with few layers of graphene and the XPS assured that about 6% of nitrogen and 4% of phosphorus co-doping into the graphene lattice through the various active forms of nitrogen and phosphorus. The large N and P content in the catalyst with all the active forms could facilitate faster ORR kinetics as well as it stability. The oxygen depolarized cathode containing electrocatalyst was fabricated and utilized in ACA cell. According to the result, the minimum cell voltage (2.01 V) was found under conditions: brine concentration 300 g/L, temperature 80 °C, pH 2 and current density 1.0 kA/m2.

Freie Borylene (R-B:) konnten bislang lediglich spektroskopisch in der Gasphase oder in Tieftemperatur-Matrices charakterisiert werden. In der letzten Zeit gelang es jedoch, einige Mono- und Di(Lewis-Base)-stabilisierte Borylene zu isolieren. In beiden Verbindungen ist das Boratom durch die formale Oxidationsstufe +I gekennzeichnet, wahrend es sich in klassischen Organoborverbindungen in der Oxidationsstufe +III befindet. Mono(Lewis-Base)-stabilisierte Borylene sind isoelektronisch zu Singulett-Carbenen, und ihre Reaktivitat ahnelt teilweise der von Ubergangsmetallen, etwa bei der Aktivierung kleiner Molekule (wie H2) und der Koordination weiterer Liganden. Di(Lewis-Base)-Borylen-Addukte sind isoelektronisch zu Aminen und Phosphanen. Im Unterschied zu Boranen, die als Elektronenakzeptoren fungieren, sind diese Spezies elektronenreich und eignen sich als Liganden fur Ubergangsmetalle.

Free borylenes (R-B:) have only been spectroscopically characterized in the gas phase or in matrices at very low temperatures. However, in recent years, a few mono- and bis(Lewis base)-stabilized borylenes have been isolated. In both of these compounds the boron atom is in the formal oxidation state +1 which contrasts with classical organoboron derivatives wherein the element is in the +3 oxidation state. Mono(Lewis base)-stabilized borylenes are isoelectronic with singlet carbenes, and their reactivity mimics to some extent that of transition metals. They can activate small molecules, such as H2, and coordinate an additional ligand; in other words, they are boron metallomimics. Bis(Lewis base)borylene adducts are isoelectronic with amines and phosphines. In contrast to boranes, which act as electron acceptors and thus Lewis acids, they are electron-rich and act as L ligands for transition metals. This mini-review highlights significant developments in this emerging field of chemistry.

Discovered in 2005, cyclic (alkyl)(amino)carbenes (CAACs) are among the most nucleophilic (σ donating) and also electrophilic (π-accepting) stable carbenes known to date. These properties allow them to activate a variety of small molecules and enthalpically strong bonds, to stabilize highly reactive main-group and transition-metal diamagnetic and paramagnetic species, and to bind strongly to metal centers, which gives rise to very robust catalysts. The most important results published up to the end of 2013 are briefly summarized, while the majority of this Review focuses on findings reported within the last three years.

A straightforward strategy allows for the synthesis of storable bicyclic (alkyl)(amino)carbenes (BICAACs), which feature enhanced σ-donating and π-accepting properties compared to monocyclic (alkyl)(amino)carbenes (CAACs). Due to the bicyclo[2.2.2]octane skeleton, the steric environment around the carbene center is different from that of CAACs and similar to that observed in classical N-heterocyclic carbenes. The different electronic properties of BICAACs as compared to CAACs allow for ligand exchange reactions not only at a metal center, but also at main group elements.

(1,3-bis[2,6-bis[di(4-tert-butylphenyl)methyl]-4-methylphenyl]imidazol-2-ylidene)CuOPh [(IPr**)CuOPh] reacts with poly(methylhydrosiloxane) as the hydride donor to afford the monomeric (IPr**)CuH complex, which was spectroscopically characterized. The latter is in equilibrium in solution with [(IPr**)CuH]2, the dimer being exclusively present in the solid state. These results support the hypothesis that copper hydride aggregates dissociate in solution. In contrast, addition of pinacolborane to [(IPr**)AgOPh] at −40 °C allows the isolation of the monomeric (IPr**)AgH complex, which was crystallographically characterized.

The Egusi Okra soup is a traditional African meal that is considered of high nutritional value and protective against weight loss. We introduce the concept of âkitchen toxicologyâ to analyse the recipe of the Egusi Okra soup and highlight possible mitigation measures for toxic and/or antinutritional effects in the wide spectrum of health and nutritional needs of HIV+/AIDS subjects. In particular, we focus on toxicants (environmental contaminants, process contaminants, substances leaching from food contact materials) dysregulating the immune status, as well as on interactions between nutrients, contaminants, and/or antinutrients which may lead to secondary/conditioned nutritional deficiencies or imbalances; in their turn, these can modulate the ability to cope with toxicants, and increase nutritional requirements. Recommendations are given for practices preserving the Egusi Okra soup from such risk factors, identifying points of particular attention during meal preparation, from purchase of raw ingredients through to food handling, cooking, storage, and consumption. The Egusi Okra soup is discussed in the context of a diet that is asked to mitigate complications (weight loss, opportunistic infections) and support antiretroviral therapy in African countries with high HIV/AIDS prevalence. The paper discusses how nutritional interventions benefit of the integration of kitchen toxicology practices in everyday life. Toxicological risk assessment is crucial to understand the history and status of the person exposed to or affected by infectious diseases. Keywords: Traditional diet, Malnutrition, Food safety, Weight loss, Immune system, Dysmetabolic diseases, Clinical toxicology, Nutrition security

Although BH3 simply coordinates the endocyclic P of (phospholidino)phosphaketene 1Dipp , the bulkier B(C6F5)3 gives rise to a zwitterionic diphosphirenium, which is a novel type of 2π-electron aromatic system as shown by the calculated NICS values. While the reaction of 1Dipp with Na[PCO(dioxane) x ] is unselective, the same reaction with the sterically bulky (phospholidino)phosphaketene 1Ar** [Ar** = 2,6-bis[di(4-tert-butylphenyl)methyl]-4-methylphenyl selectively affords a sodium bridged dimer containing a hitherto unknown λ3,λ5,λ3-triphosphete core. The latter formally results from "P-" addition to a 1,3-P/C-dipole. Similarly, adamantyl isonitrile adds to 1Dipp giving a 4-membered phosphacycle. In contrast to 1, the phosphaketene derived from the electrophilic diazaphospholidine-4,5-dione is unstable and reacts with a second molecule of Na[PCO(dioxane) x ] to afford a 1,3,4-oxadiphospholonide derivative.

The aim of this survey was to identify the active ingredients of phytosanitary products generally used in the market-gardening, to evaluate the behavior of market gardeners, environmental and sanitary risks link to the use of phytosanitary products. Results revealed that 8 actives ingredients are regularly used: paraquat, atrazine, glyphosate, chlorpyrifos-ethyl, cypermethrin, maneb, mancozeb and diuron. The contamination of running water and rivers is caused by the fact that 81.25% of them are washing their pulverization equipments in these last ones. Moreover, 72.90% release empty packages of pesticides in the farm which will be carried away by running water. 59.09% adopt the overdose strategy in case of insufficient treatment. The inadequate equipment of protection and the consumption of surrounding water by 51.10% represent a danger for the health of market gardeners. Thus, headache and stomachache are the most recorded intoxications.

Chiral acetyl-protected aminoalkyl quinoline (APAQ) ligands were recently discovered to afford highly active and enantioselective palladium catalysts for the arylation of methylene C(sp3)-H bonds, and herein, we investigate the origins of these heightened properties. Unprecedented amide-bridged APAQ-Pd dimers were predicted by density functional theory (DFT) calculations and were confirmed by single-crystal X-ray diffraction studies. Comparison of structural features between APAQ-Pd complexes and an acetyl-protected aminoethylpyridine APAPy-Pd complex strongly suggests that the high activity of the former originates from the presence of the quinoline ring, which slows the formation of the off-cycle palladium dimer. Furthermore, steric topographic maps for a representative subset of monomeric, monoligated palladium complexes allowed us to draw a unique parallel between the three-dimensional structures of these catalysts and their reported asymmetric induction in β-C(sp3)-H bond arylation reactions. Finally, cooperative noncovalent interactions present between the APAQ ligand and the substrate were identified as a crucial factor for imparting selectivity between chemically equivalent methylenic C(sp3)-H bonds prior to concerted metalation deprotonation activation.

Chiral acetyl-protected aminoalkyl quinoline (APAQ) ligands were recently discovered to afford highly active and enantioselective palladium catalysts for the arylation of methylene C(sp

Summary H/D exchange at formyl groups is the most direct approach for the synthesis of deuterated aldehydes. Platinum-group metal complexes have been employed to catalyze this transformation, with significant substrate scope limitations. Although N-heterocyclic carbenes can also activate the C–H bond of aldehydes through the formation of Breslow intermediates, benzoin condensation and other C–C-bond-forming pathways have so far outpaced synthetically useful H/D exchange. Investigation of the reaction of aldehydes with 1,2,3-triazolylidenes has revealed the reversible formation of Breslow intermediates and the inhibition of the condensation steps in methanol solvent. 1,2,3-Triazolylidenes catalyze the H/D exchange of aryl, alkenyl, and alkyl aldehydes in high yields and deuterium incorporation levels using deuterated methanol as an affordable D source. The unique properties of these mesoionic carbenes (MICs) enable a streamlined preparation of deuterated synthetic intermediates and pharmacophores that are highly valuable as mechanistic and metabolic probes.

International audience; The popularity of NHCs in transition metal catalysis has prompted the development of chiral versions as electron-rich neutral stereodirecting ancillary ligands for enantioselective transformations. Herein we demonstrate that cyclic (alkyl)(amino)carbene (CAAC) ligands can also engage in asymmetric transformations, thereby expanding the toolbox of available chiral carbenes.

It has been previously demonstrated that stable singlet electrophilic carbenes can behave as metal surrogates in the activation of strong E-H bonds (E = H, B, N, Si, P), but it was believed that these activations only proceed through an irreversible activation barrier. Herein we show that, as is the case with transition metals, the steric environment can be used to promote reductive elimination at carbon centers.

A systematic study is presented on the physical and photophysical properties of isoelectronic and isostructural Cu, Ag, and Au complexes with a common amide (N-carbazolyl) and two different carbene ligands (i.e., CAAC = (5 R,6 S)-2-(2,6-diisopropylphenyl)-6-isopropyl-3,3,9-trimethyl-2-azaspiro[4.5]decan-2-ylidene, MAC = 1,3-bis(2,6-diisopropylphenyl)-5,5-dimethyl-4-keto-tetrahydropyridylidene). The crystal structures of the (carbene)M

In this study, removal of Cr (VI) from aqueous solutions by adsorption onto clay modified by sodium chloride and clay modified by aluminum hydroxide was investigated as a function of pH, contact time, adsorbent dosage, initial metal concentration and temperature. Time-dependent experimental studies showed that the adsorption quantity of Cr (VI) increases with initial concentration and decreasing adsorbent dosage. The equilibrium time of 10 and 40 min was observed clay modified by sodium chloride and clay modified by aluminum hydroxide (CSC and CAH) and maximum adsorption was favored at pH 3. The Cr (VI) removal using 0.1 g of adsorbent was more than 90%. This dosage (0.1 g) was considered as the optimum dosage to remove Cr (VI) aqueous solutions. Experimental data were investigated by two adsorption isotherms models (Langmuir and Freundlich). Applicability of isotherm equation to describe the adsorption process was analysed by the correlation coefficients values, R2. Langmuir and Freundlich models show best fit with R2 values superior of 0.95. The mechanism of adsorption of Cr (VI) is therefore based on the assumption of the kinetic model of pseudo-second order in two steps. Thermodynamic parameters such as ∆H°, ∆G° and ∆S° demonstrated that adsorption mechanism of Cr (VI) onto clay modified by sodium chloride and clay modified by aluminum hydroxide, physisorption, spontaneous and exothermic in the ranges of temperature of 203-333K.

The coordination of Ge9 Zintl clusters at (carbene)CuI moieties is explored, and the complexes [(CAAC)Cu]2[η3-Ge9{Si(TMS)3}2] (1), (CAAC)Cu[η3-Ge9{Si(TMS)3}3] (2), and (MIC)Cu[η3-Ge9{Si(TMS)3}3] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge9R2]2- and [Ge9R3]- [R = Si(TMS)3] cluster ligands, respectively, and yields complexes of (carbene)CuI (carbene = CAAC, MIC) moieties exhibiting η3-coordination modes of the Ge9 deltahedron to the Cu atom. In 1, [Ge9R2]2- acts as a η3-bridging unit for two (CAAC)CuI moieties, and 2 and 3 feature single (carbene)CuI (CAAC and MIC) fragments η3-connected to [Ge9R3]- units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge3 triangular faces for all (carbene)CuIGe9 complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [1H, 13C{1H}, and 29Si{1H}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge9 clusters with carbene ligands at CuI atoms.