Showing papers in "Chemistry: A European Journal in 2015"
TL;DR: The interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently are described and highlighted.
Abstract: This article aims to show the identity of “circularly polarized luminescent active simple organic molecules” as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.
655 citations
TL;DR: This Concept focuses on BN-substituted polycyclic aromatics with fused structures, and reviews their synthesis, photophysical, and redox properties, as well as their applications in organic electronics.
Abstract: Replacement of CC unit with its isoelectronic BN unit in aromatics provides a new class of molecules with appealing properties, which have attracted great attention recently. In this Concept, we focus on BN-substituted polycyclic aromatics with fused structures, and review their synthesis, photophysical, and redox properties, as well as their applications in organic electronics. We also present challenging synthetic targets, large BN- substituted polycyclic aromatics, such as regioregular BN heterosuperbenzenes, which can be viewed as BN-doped nanographenes. Finally, we propose an atomically precise bottom-up synthesis of structurally well-defined BN-doped graphenes.
312 citations
TL;DR: It is shown that Tb-MOF can selectively sense Fe(3+) and Al(3%) ions from mixed metal ions in water through different detection mechanisms and exhibits high sensitivity for 2,4,6-trinitrophenol (TNP) in the presence of other nitro aromatic compounds in aqueous solution by luminescence quenching experiments.
Abstract: A water-stable luminescent terbium-based metal-organic framework (MOF), {[Tb(L1 )1.5 (H2 O)]⋅3 H2 O}n (Tb-MOF), with rod-shaped secondary building units (SBUs) and honeycomb-type tubular channels has been synthesized and structurally characterized by single-crystal X-ray diffraction. The high green emission intensity and the microporous nature of the Tb-MOF indicate that it can potentially be used as a luminescent sensor. In this work, we show that Tb-MOF can selectively sense Fe(3+) and Al(3+) ions from mixed metal ions in water through different detection mechanisms. In addition, it also exhibits high sensitivity for 2,4,6-trinitrophenol (TNP) in the presence of other nitro aromatic compounds in aqueous solution by luminescence quenching experiments.
298 citations
TL;DR: Progress in their use as catalysts for (de)hydrogenation and transfer ( de)Hydrogenation reactions during the last four years is covered in this Minireview.
Abstract: Pincer complexes are becoming increasingly important for organometallic chemistry and organic synthesis. Since numerous applications for such catalysts have been developed in recent decades, this Minireview covers progress in their use as catalysts for (de)hydrogenation and transfer (de)hydrogenation reactions during the last four years. Aside from noble-metal-based pincer complexes, the corresponding base metal complexes are also highlighted and their applications summarized.
293 citations
TL;DR: An accurate sensing of TNP, widely recognized as a harmful environmental contaminant in water media, establishes this new strategic approach as one of the frontiers to tackle present-day security and health concerns in a real-time scenario.
Abstract: Highly selective and sensitive aqueous-phase detection of nitro explosive 2,4,6-trinitrophenol (TNP) by a hydrolytically stable 3D luminescent metal-organic framework is reported. The compound senses TNP exclusively even in the presence of other nitro-compounds, with an unprecedented sensitivity in the MOF regime by means of strategic deployment of its free amine groups. Such an accurate sensing of TNP, widely recognized as a harmful environmental contaminant in water media, establishes this new strategic approach as one of the frontiers to tackle present-day security and health concerns in a real-time scenario.
288 citations
261 citations
TL;DR: In this Minireview, the most relevant methods for the introduction of difluoromethylated building blocks are summarized and special attention is paid to explanation of the reaction mechanism.
Abstract: Fluorine chemistry is a field undergoing tremendous expansion. Although much attention has been paid to the introduction of the fluorine atom and the CF3 group, less interest has been devoted to the introduction of functionalized fluorinated building blocks, in sharp contrast with the high versatility of the fluorinated products. In this Minireview, the most relevant methods for the introduction of difluoromethylated building blocks are summarized. Access to difluoromethylated arenes, alkenes, and alkynes is highlighted and special attention is paid to explanation of the reaction mechanism.
255 citations
TL;DR: It is recommended to use the term gold carbene to describe goldcarbene-like intermediates, regardless of whether the carbene or carbocation extreme resonance dominates.
Abstract: By reviewing the recent progress on the elucidation of the structure of gold carbenes and the definitions of metal carbenes and carbenoids, we recommend to use the term gold carbene to describe gold carbene-like intermediates, regardless of whether the carbene or carbocation extreme resonance dominates. Gold carbenes, because of the weak metal-to-carbene π-back-donation and their strongly electrophilic reactivity, could be classified into the broader family of Fischer carbenes, although their behavior and properties are very specific.
233 citations
TL;DR: This article explores selected advances in methods for the preparation and use of hyperpolarized contrast agents, many of which are already at or near the phase of their clinical validation in patients.
Abstract: Recent developments in NMR hyperpolarization have enabled a wide array of new in vivo molecular imaging modalities, ranging from functional imaging of the lungs to metabolic imaging of cancer. This Concept article explores selected advances in methods for the preparation and use of hyperpolarized contrast agents, many of which are already at or near the phase of their clinical validation in patients.
225 citations
TL;DR: A flexible electrode, based on carbon cloth substrate and iron phosphide nanotubes coated with an iron oxide/phosphate layer, is shown to catalyze overall water splitting and demonstrates remarkable electrocatalytic activity for both the hydrogen evolution reaction (HER) and the oxygen evolution Reaction (OER) at modest overpotentials.
Abstract: The design of cheap and efficient water splitting systems for sustainable hydrogen production has attracted increasing attention. A flexible electrode, based on carbon cloth substrate and iron phosphide nanotubes coated with an iron oxide/phosphate layer, is shown to catalyze overall water splitting. The as-prepared flexible electrode demonstrates remarkable electrocatalytic activity for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) at modest overpotentials. The surface iron oxide/phosphate, which is formed in situ, is proposed to improve the HER activity by facilitating the water-dissociation step and serves directly as the catalytically-active component for the OER process.
224 citations
TL;DR: The results showed that doping of P in graphene exhibited significant improvement in terms of specific capacitance and cycling stability, compared with undoped graphene electrode.
Abstract: Phosphorus-doped (P-doped) graphene with the P doping level of 1.30 at % was synthesized by annealing the mixture of graphene and phosphoric acid. The presence of P was confirmed by elemental mapping and X-ray photoelectron spectroscopy, while the morphology of P-doped graphene was revealed by using scanning electron microscopy and transmission electron microscopy. To investigate the effect of P doping, the electrochemical properties of P-doped graphene were tested as a supercapacitor electrode in an aqueous electrolyte of 1 M H2SO4. The results showed that doping of P in graphene exhibited significant improvement in terms of specific capacitance and cycling stability, compared with undoped graphene electrode. More interestingly, the P-doped graphene electrode can survive at a wide voltage window of 1.7 V with only 3 % performance degradation after 5000 cycles at a current density of 5 A g−1, providing a high energy density of 11.64 Wh kg−1 and a high power density of 831 W kg−1.
TL;DR: These multifunctional MOF materials combine optical-sensing, adsorption, and sensitization properties, thus are very useful in many potential applications and have proved to be reusable.
Abstract: A series of highly luminescent-active metal-organic frameworks (MOFs) 1-3 with hierarchical pores have been rationally constructed and fully characterized. The predesigned semi-rigid hexacarboxylate ligand hexa[4-(carboxyphenyl)oxamethyl]-3-oxapentane acid (H6L) has been adapted with various space-directed Ndonors (i.e., 2,2'-bipyridine, 4,4-di(1H-imidazol-1-yl)-1,1-biphenyl, and 1,3,5-tri(1H-imidazol-1-yl)benzene) from a bidentate V-shape to a tridentate Y-shape. This family of multifunctional MOF materials represents a variety of potential applications in the following aspects: first, as luminescent sensors that show a fast and sensitive detection for pollutant CrO42- and Cr2O72- ions in aqueous media; second, as adsorbents that can rapidly remove harmful organic dyes; third, as an antenna that can effectively sensitize visible-light-emitting Tb3+ ions. These multifunctional MOF materials combine optical-sensing, adsorption, and sensitization properties, thus are very useful in many potential applications. Furthermore, these materials have proved to be reusable.
TL;DR: This is the first MOF that can serve as a dual functional fluorescent sensor for selectively detecting trace amounts of TNP and Cu(2+) and show high sensitivity and selectivity of the fluorescence response of 1 to TNP.
Abstract: A luminescent cadmium–pamoate metal–organic framework, [Cd2(PAM)2(dpe)2(H2O)2]⋅0.5(dpe) (1), has been synthesized under hydrothermal conditions by using π-electron-rich ligands 4,4′-methylenebis(3-hydroxy-2-naphthalenecarboxylic acid) (H2PAM) and 1,2-di(4-pyridyl)ethylene (dpe). Its structure is composed of both mononuclear and dinuclear CdII building units, which are linked by the PAM and dpe ligands, resulting in a (4,8)-connected 3D framework. The π-conjugated dpe guests are located in a 1D channel of 1. The strong emission of 1 could be quenched efficiently by trace amounts of 2,4,6-trinitrophenol (TNP), even in the presence of other competing analogues such as 4-nitrophenol, 2,6-dinitrotoluene, 2,4-dinitrotoluene, nitrobenzene, 1,3-dinitrobenzene, hydroquinone, dimethylbenzene, and bromobenzene. The high sensitivity and selectivity of the fluorescence response of 1 to TNP shows that this framework could be used as an excellent sensor for identifying and quantifying TNP. In the same manner, 1 also exhibits superior selectivity and sensitivity towards Cu2+ compared with other metal ions such as Zn2+, Mn2+, Mg2+, K+, Na+, Ni2+, Co2+, and Ca2+. This is the first MOF that can serve as a dual functional fluorescent sensor for selectively detecting trace amounts of TNP and Cu2+.
TL;DR: The first part addresses the development of new metal-based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselectives ROP metal catalysts to control the monomer sequence inCopolymers.
Abstract: Metal-based catalysts and initiators have played a pivotal role in the ring-opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis-stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal-based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts-primarily metal-based catalysts, but also organocatalysts-that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.
TL;DR: A mesoporous flake-like manganese-cobalt composite oxide (MnCo2O4) is synthesized successfully through the hydrothermal method and evaluated as the anode material for lithium-ion batteries.
Abstract: A mesoporous flake-like manganese-cobalt composite oxide (MnCo2O4) is synthesized successfully through the hydrothermal method. The crystalline phase and morphology of the materials are characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller methods. The flake-like MnCo2O4 is evaluated as the anode material for lithium-ion batteries. Owing to its mesoporous nature, it exhibits a high reversible capacity of 1066 mA h g(-1), good rate capability, and superior cycling stability. As an electrode material for supercapacitors, the flake-like MnCo2O4 also demonstrates a high supercapacitance of 1487 F g(-1) at a current density of 1 A g(-1), and an exceptional cycling performance over 2000 charge/discharge cycles.
TL;DR: The new covalent organic framework material combines permanent micropores, high crystallinity, good thermal and chemical stability, and abundant heteroatom activated sites in the skeleton to exhibit remarkable carbon dioxide uptake and methane uptake and high CO2 /N2 selectivity.
Abstract: A azine-linked covalent organic framework, COF-JLU2, was designed and synthesized by condensation of hydrazine hydrate and 1,3,5-triformylphloroglucinol under solvothermal conditions for the first time. The new covalent organic framework material combines permanent micropores, high crystallinity, good thermal and chemical stability, and abundant heteroatom activated sites in the skeleton. COF-JLU2 possesses a moderate BET surface area of over 410 m(2) g(-1) with a pore volume of 0.56 cm(3) g(-1) . Specifically, COF-JLU2 displays remarkable carbon dioxide uptake (up to 217 mg g(-1) ) and methane uptake (38 mg g(-1) ) at 273 K and 1 bar, as well as high CO2 /N2 (77) selectivity. Furthermore, we further highlight that it exhibits a higher hydrogen storage capacity (16 mg g(-1) ) than those of reported COFs at 77 K and 1 bar.
TL;DR: NanoMOFs were ranked according to their respective in vivo toxicity (in terms of the amount and severity of phenotypic changes observed in the treated zebrafish embryos), which varied widely, and show different levels of toxicity of these materials.
Abstract: Metal-organic frameworks (MOFs) are among the most attractive porous materials available today. They have garnered much attention for their potential utility in many different areas such as gas storage, separation, catalysis, and biomedicine. However, very little is known about the possible health or environmental risks of these materials. Here, the results of toxicity studies on sixteen representative uncoated MOF nanoparticles (nanoMOFs), which were assessed for cytotoxicity to HepG2 and MCF7 cells in vitro, and for toxicity to zebrafish embryos in vivo, are reported. Interestingly, there is a strong correlation between their in vitro toxicity and their in vivo toxicity. NanoMOFs were ranked according to their respective in vivo toxicity (in terms of the amount and severity of phenotypic changes observed in the treated zebrafish embryos), which varied widely. Altogether these results show different levels of toxicity of these materials; however, leaching of solubilized metal ions plays a main role.
TL;DR: The chemical aspects regarding lipid A and its role in innate immunity are described and discussed, from the (bio)synthesis, isolation and characterization to the molecular recognition at the atomic level.
Abstract: In many Gram-negative bacteria, lipopolysaccharide (LPS) and its lipid A moiety are pivotal for bacterial survival. Depending on its structure, lipid A carries the toxic properties of the LPS and acts as a potent elicitor of the host innate immune system via the Toll-like receptor 4/myeloid differentiation factor 2 (TLR4/MD-2) receptor complex. It often causes a wide variety of biological effects ranging from a remarkable enhancement of the resistance to the infection to an uncontrolled and massive immune response resulting in sepsis and septic shock. Since the bioactivity of lipid A is strongly influenced by its primary structure, a broad range of chemical syntheses of lipid A derivatives have made an enormous contribution to the characterization of lipid A bioactivity, providing novel pharmacological targets for the development of new biomedical therapies. Here, we describe and discuss the chemical aspects regarding lipid A and its role in innate immunity, from the (bio)synthesis, isolation and characterization to the molecular recognition at the atomic level.
TL;DR: A donor-acceptor-type fluorophore containing a twisted diphenylacrylonitrile and triphenylamine has been developed by using the Suzuki reaction and indicates typical intramolecular charge-transfer properties.
Abstract: A donor-acceptor-type fluorophore containing a twisted diphenylacrylonitrile and triphenylamine has been developed by using the Suzuki reaction. The system indicates typical intramolecular charge-transfer properties. Upon mechanical grinding or hydrostatic pressure, the fluorophore reveals a multicolored fluorescence switching. Interestingly, a fluorescence color transition from green to red was clearly observed, and the change of photoluminescent (PL) wavelength gets close to 111 nm. The mechanisms of high-contrast mechanochromic behavior are fully investigated by techniques including powder XRD, PL lifetime, high-pressure PL lifetime, and Raman spectra analysis. The tremendous PL wavelength shift is attributed to gradual transition of excited states from the local excited state to the charge-transfer state.
TL;DR: From the X-ray diffraction and differential scanning calorimetry analyses, it was confirmed that the MFC property of boron ketoiminates should be derived from a phase transition between crystalline and amorphous states.
Abstract: We report a series of mechanofluorochromic (MFC) compounds based on organoboron complexes with aggregation-induced emission (AIE) characteristics We synthesized a variety of boron ketoiminates and investigated the effect of the substituents on the optical properties by altering the end groups in the compounds The synthesized boron ketoiminates showed AIE properties and MFC behavior Interestingly, the hypsochromic and bathochromic shifts of the emission bands individually observed for boron ketoiminates depended on the chemical structures of the end groups From the X-ray diffraction and differential scanning calorimetry analyses, it was confirmed that the MFC property of boron ketoiminates should be derived from a phase transition between crystalline and amorphous states In addition, the direction of the peak shifts of the emission bands was controlled by the degree of steric hindrance of the end group
TL;DR: Recent developments on the rational design of electron-rich self-assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase are summarized.
Abstract: Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO2 -containing electron-deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron-rich self-assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several π-electron-rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal-ligand coordination-bonding interactions, with enough internal space to accommodate electron-deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives.
TL;DR: Efficient, scalable cobalt-catalyzed redox-neutral [4+2] annulation of readily available oximes and alkyne is reported, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.
Abstract: Efficient, scalable cobalt-catalyzed redox-neutral [4+2] annulation of readily available oximes and alkyne is reported. The developed synthetic methodology is widely applicable and tolerates various functional groups including heterocycles. A stable Cp*Co(III) neutral complex is employed as the catalyst for this redox-neutral [4+2] annulation reaction, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.
TL;DR: The addition of water or methanol to the electrolyte allows a shift of oxidation potentials in a specific range, creating suitable systems for selective anodic cross-coupling reactions, and this driving force for selectivity in oxidative coupling might also explain previous findings using HFIP and hypervalent iodine reagents.
Abstract: Solvents such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) with a high capacity for donating hydrogen bonds generate solvates that enter into selective cross-coupling reactions of aryls upon oxidation. When electric current is employed for oxidation, reagent effects can be excluded and a decoupling of nucleophilicity from oxidation potential can be achieved. The addition of water or methanol to the electrolyte allows a shift of oxidation potentials in a specific range, creating suitable systems for selective anodic cross-coupling reactions. The shift in the redox potentials depends on the substitution pattern of the substrate employed. The concept has been expanded from arene-phenol to phenol-phenol as well as phenol-aniline cross-coupling. This driving force for selectivity in oxidative coupling might also explain previous findings using HFIP and hypervalent iodine reagents.
TL;DR: This work aims to highlight some recent studies showcasing the multi-stimuli-responsive character of these polymers, which are still relatively little known compared to their single-stimulus-responsive counterpart.
Abstract: Stimuli-responsive materials are of immense importance because of their ability to undergo alteration of their properties in response to their environment. The properties of such materials can be tuned by subtle adjustments in temperature, pH, light, and so forth. Among such smart materials, multi-stimuli-responsive polymeric materials are of pronounced significance as they offer a wide range of applications and their properties can be tuned through several mechanisms. Here, we aim to highlight some recent studies showcasing the multi-stimuli-responsive character of these polymers, which are still relatively little known compared to their single-stimuli-responsive counterpart.
TL;DR: In this paper, the synthesis and anode application for sodium-ion batteries (SIBs) of WS2 nanowires (WS2 NWs) were reported. And the as-prepared WS2NWs were evaluated as anode materials of SIBs in two potential windows of 0.01-2.5 V and 0.5-3 V.
Abstract: We report the synthesis and anode application for sodium-ion batteries (SIBs) of WS2 nanowires (WS2 NWs). WS2 NWs with very thin diameter of ≈25 nm and expanded interlayer spacing of 0.83 nm were prepared by using a facile solvothermal method followed by a heat treatment. The as-prepared WS2 NWs were evaluated as anode materials of SIBs in two potential windows of 0.01-2.5 V and 0.5-3 V. WS2 NWs displayed a remarkable capacity (605.3 mA h g(-1) at 100 mA g(-1) ) but with irreversible conversion reaction in the potential window of 0.01-2.5 V. In comparison, WS2 NWs showed a reversible intercalation mechanism in the potential window of 0.5-3 V, in which the nanowire-framework is well maintained. In the latter case, the interlayers of WS2 are gradually expanded and exfoliated during repeated charge-discharge cycling. This not only provides more active sites and open channels for the intercalation of Na(+) but also facilitates the electronic and ionic diffusion. Therefore, WS2 NWs exhibited an ultra-long cycle life with high capacity and rate capability in the potential window of 0.5-3 V. This study shows that WS2 NWs are promising as the anode materials of room-temperature SIBs.
TL;DR: The toxicological effects of black phosphorus are found to be dose-dependent and generally intermediate between that of graphene oxides and exfoliated transition-metal dichalcogenides (MoS2, WS2, WSe2).
Abstract: Black phosphorus (BP), the latest addition to the family of 2D layered materials, has attracted much interest owing to potential optoelectronics, nanoelectronics, and biomedicine applications. Little is known about its toxicity, such as whether it could be as toxic as white phosphorus. In response to the possibility of BP employment into commercial products and biomedical devices, its cytotoxicity to human lung carcinoma epithelial cells (A549) was investigated. Following a 24 h exposure of the cells with different BP concentrations, cell viability assessments were conducted using water-soluble tetrazolium salt (WST-8) and methylthiazolyldiphenyltetrazolium bromide (MTT) assays. The toxicological effects were found to be dose-dependent, with BP reducing cell viabilities to 48% (WST-8) and 34% (MTT) at 50 μg mL(-1) exposure. This toxicity was observed to be generally intermediate between that of graphene oxides and exfoliated transition-metal dichalcogenides (MoS2, WS2, WSe2). The relatively low toxicity paves the way to utilization of black phosphorus.
TL;DR: A superior Na3 V2 (PO4 )3 -based nanocomposite (NVP/C/rGO) has been successfully developed by a facile carbothermal reduction method using one most-common chelator as both sodium and nitrogen-doped carbon sources for the first time.
Abstract: A superior Na3 V2 (PO4 )3 -based nanocomposite (NVP/C/rGO) has been successfully developed by a facile carbothermal reduction method using one most-common chelator, disodium ethylenediamintetraacetate [Na2 (C10 H16 N2 O8 )], as both sodium and nitrogen-doped carbon sources for the first time. 2D-reduced graphene oxide (rGO) nanosheets are also employed as highly conductive additives to facilitate the electrical conductivity and limit the growth of NVP nanoparticles. When used as the cathode material for sodium-ion batteries, the NVP/C/rGO nanocomposite exhibits the highest discharge capacity, the best high-rate capabilities and prolonged cycling life compared to the pristine NVP and single-carbon-modified NVP/C. Specifically, the 0.1 C discharge capacity delivered by the NVP/C/rGO is 116.8 mAh g(-1) , which is obviously higher than 106 and 112.3 mAh g(-1) for the NVP/C and pristine NVP respectively; it can still deliver a specific capacity of about 80 mAh g(-1) even at a high rate up to 30 C; and its capacity decay is as low as 0.0355 % per cycle when cycled at 0.2 C. Furthermore, the electrochemical impedance spectroscopy was also implemented to compare the electrode kinetics of all three NVP-based cathodes including the apparent Na diffusion coefficients and charge-transfer resistances.
TL;DR: C-H/N-O functionalizations by cobalt(III) catalysis allowed the expedient synthesis of a broad range of isoquinolines and internal and challenging terminal alkynes proved to be viable substrates for an isohypsic annulation.
Abstract: C-H/N-O functionalizations by cobalt(III) catalysis allowed the expedient synthesis of a broad range of isoquinolines. Thus, internal and challenging terminal alkynes proved to be viable substrates for an isohypsic annulation, which was shown to proceed by a facile C-H cobaltation.
TL;DR: 6-arylpurine compounds, which often exhibit high potency in antimycobacterial, cytostatic, and anti-HCV activities, can be smoothly amidated, thus offering a mild protocol for their late stage functionalization.
Abstract: A cationic cobalt(III)-catalyzed direct C-H amidation of unactivated (hetero)arenes and alkenes by using 1,4,2-dioxazol-5-ones as the amidating reagent has been developed. This transformation proceeds efficiently under external oxidant-free conditions with a broad substrate scope. Moreover, 6-arylpurine compounds, which often exhibit high potency in antimycobacterial, cytostatic, and anti-HCV activities, can be smoothly amidated, thus offering a mild protocol for their late stage functionalization.
TL;DR: Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles-namely, aryl halides and diazonium salts-demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources.
Abstract: Lewis base adducts of tetra-alkoxy diboron compounds, in particular bis(pinacolato)diboron (B2 pin2 ), have been proposed as the active source of nucleophilic boryl species in metal-free borylation reactions. We report the isolation and detailed structural characterization (by solid-state and solution NMR spectroscopy and X-ray crystallography) of a series of anionic adducts of B2 pin2 with hard Lewis bases, such as alkoxides and fluoride. The study was extended to alternative Lewis bases, such as acetate, and other diboron reagents. The B(sp(2) )-B(sp(3) ) adducts exhibit two distinct boron environments in the solid-state and solution NMR spectra, except for [(4-tBuC6 H4 O)B2 pin2 ](-) , which shows rapid site exchange in solution. DFT calculations were performed to analyze the stability of the adducts with respect to dissociation. Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles-namely, aryl halides and diazonium salts-demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources.