Regio‐ and Stereospecific Copper‐Catalyzed S N 2’ Substitution Reaction of Propargyl Esters with Polyfluoroaryl Zinc Reagents

Although trifluoromethylthiolated compounds have privileged applications in pharmaceuticals and agrochemicals, efficient strategies for the asymmetric construction of Csp3–SCF3 bonds are limited. S...

Stereospecific and stereoconvergent nucleophilic substitution reactions at tertiary carbon centers

5-Hydroxymethylfurfural (HMF) is one of the versatile platform molecules that can be derived from biomass, and a promising starting substrate for producing 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). DFF is a platform chemical with applications in pharmaceuticals, macrocyclic ligands, and functional polymeric materials. Importantly, FDCA is being considered as a potential alternative to replace terephthalic acid for producing the bioplastic polyethylene furanoate, instead of polyethylene terephthalate, by blending with ethylene glycol. A significant number of studies have focused on the oxidation of HMF to FDCA with metal-containing heterogeneous catalysts in both aqueous and organic media in the presence of peroxides/air/molecular oxygen as the oxidant. In this regard, articles have recently been published related to HMF oxidation with base (nonprecious)-metal-containing catalysts that exhibit appealing activity towards DFF or FDCA in terms of yield. Thus, this Minireview focuses on recent developments in efficient transformations of HMF to DFF and FDCA with base-metal-containing heterogeneous catalysts in aqueous and organic media. This review further focuses on the direct transformation of glucose/fructose to DFF and/or FDCA with nonprecious-metal-containing catalysts in various solvents. Photocatalytic approaches for HMF oxidation with nonprecious metal- containing catalysts are also briefly discussed.

Succinimide motifs are recognized as privileged cores in anticonvulsants and antipsychotics such as phensuximide, ethosuximide, and lurasidone. These succinimides can be readily converted into pharmaceutically important pyrrolidines and γ-lactam scaffolds, making them highly promising compounds in drug discovery. Nitroarenes are also important chemical feedstocks and have attracted increased attention owing to their versatile applications in pharmaceuticals, functional materials, and agricultural pharmacology. Therefore, directly combining succinimides with nitroarenes is a valuable approach for efficiently constructing novel succinimide-linked nitroarene frameworks. We herein report the site-selective addition of the succinimide scaffold to various nitroarenes via nitro-directed ortho-C-H alkylation using maleimides under rhodium(III) catalysis. The versatility of the developed protocol is demonstrated through nitro-group reduction, reductive cyclization of the synthesized products, and selective modifications of the succinimide framework. Mechanistic studies, including deuterium-labeling and kinetic isotope effect experiments, helped elucidate a plausible reaction mechanism.

Functionalized biaryl-containing motifs are among the most valuable synthetic scaffolds in organic chemistry with wide ranging commercial applications in pharmaceuticals, functional materials, and agrochemicals. Recently, there has been tremendous progress in the development of methods for functional-group-tolerant, cost-effective, and atom-economic ruthenium-catalyzed C–H arylation, providing attractive catalytic alternatives to traditional C–H functionalization and cross-coupling approaches. New ruthenium-catalyzed C–H arylation reactions have resulted in the development of attractive and highly efficient synthetic approaches to functionalized biaryls unavailable by other methods. New mechanistic manifolds have emerged, thus opening prospects for the development of a broad range of novel reactions. Strategies for the use of ruthenium catalysis in complex synthesis, including industrial applications, have been reported, validating the synthetic potential of this mode of reactivity. The development of new...

Aminomethylphenol molecules have wider applications in pharmaceuticals, agrochemicals, plant protection and promising functional materials. The development of an efficient and practical method to prepare this class of compound is highly desirable from both environmental and economical points of view. In order to establish an effective synthetic method for preparing aminomethylphenol derivatives, the Petasis borono-Mannich reaction of salicylaldehyde, phenylboronic acid and 1,2,3,4- tetrahydroisoquinoline was selected as a model reaction. A variety of reaction conditions are investigated, including solvent and temperature. The generality and limitation of the established method were also evaluated. It was found that model reaction can be carried out in cyclopentyl methyl ether at 80 oC under catalyst-free conditions. This protocol, with broad substrate applicability, the reaction of various arylboronic acid, secondary amine and salicylaldehyde proceeded smoothly under optimal reaction conditions to afford various aminomethylphenol derivatives in high yields. A practical, scalable, and high-yielding synthesis of aminomethylphenol derivatives was successfully accomplished. A catalyst-free practical method for the synthesis of minomethylphenol derivatives based on Petasis borono-Mannich (PBM) reaction of various arylboronic acid, secondary amine and salicylaldehyde in cyclopentyl methyl ether has been developed. The salient features of this protocol are avoidance of any additive/catalyst and toxic organic solvents, use of cyclopentyl methyl ether as the reaction medium, clean reaction profiles, easy operation, and high to excellent yield.

This work reflects both the synthesis and the characterization of a novel catalyst obtained by functionalizing geopolymers through the grafting of an amino group onto their surface. Expanded perlite (PE) was chosen as the primary raw material due to its high availability, low cost, and environmental compatibility. Its favorable structure and reactivity with alkaline agents make it an excellent candidate for geopolymer (GP) formation. Subsequently, 3-aminopropyltrimethoxysilane (APTMS) was grafted onto the GP surface to obtain a modified geopolymer catalyst (GPM). The modification enhanced the geopolymer's functionality, making it efficient, eco-friendly, safe, and reusable. Characterization by XRD, SEM, EDX, and TGA confirmed successful grafting and improved the thermal stability of the resulting GPM catalyst. The catalytic efficacy of this novel catalyst was explored for the first time in the synthesis of substituted 4H-chromene, using a direct, straightforward, and highly efficient one-step procedure within a multicomponent reaction. This reaction combines various aldehydes, malononitrile, and β-diketone in ethanol at ambient temperature. The catalyst enabled excellent yields ranging from 90 to 98% under mild and eco-friendly conditions. The resulting 4H-chromene derivatives were confirmed via melting point, FT-IR, 1H NMR, and 13C NMR analyses. Moreover, the GPM catalyst demonstrated high recyclability, maintaining over 90% of its catalytic activity after five consecutive cycles. To complement the experimental findings, DFT calculations (B3LYP/6-31G(d,p)) were performed, providing insight into the electronic properties, including frontier molecular orbitals and molecular electrostatic potentials. These results highlighted the most reactive molecular regions, supporting the potential of the synthesized chromene derivatives in pharmaceutical applications and drug design. Overall, the study demonstrates the effectiveness, sustainability, and broader applicability of the newly developed heterogeneous GPM catalyst. These findings highlight the potential of geopolymer-based catalysts as sustainable alternatives in green chemistry and showcase their versatility for future applications in synthetic and medicinal chemistry.

High internal phase emulsions (HIPEs) are usually defined as a kind of superconcentrated emulsions, in which the minimum internal phase volume fraction reaches to 0.74. Comparing with traditional emulsions, high internal phase emulsions (HIPEs) tend to be highly viscous, solid-like emulsions because of their higher internal phase volume fraction. Thus, focusing on their microstructure, the shape of the oil droplets turned from spheres to irregular polyhedrons separated by a continuous phase film, leading to the deformation of the inner phase droplets. Obviously, the selection of suitable and effective stabilizers based on different stabilization mechanisms is vital for the emulsification process. Up to now, mainly three types of stabilizers based on dissimilar stabilization mechanisms have been successfully developed, including traditional surfactants, solid particles, and low molecular weight or macromolecular gelators. Given that the unique structural features, the wide applicability of HIPEs in pharmaceutical formulations, controlled-release deliverers, cosmetics industries, cold chain logistics and fatty food products has received considerable attentions. Moreover, owing to the characteristics of high viscosity and large interface film area, it is feasible to use high internal phase emulsion as a template to prepare porous functional materials, and the polyhedral structure of the internal droplets endows the final obtained porous material with higher specific surface area, higher porosity and lighter weight. Comparing with the other traditional methods, such as microemulsion method, chemical corrosion method, phase separation method, and so on, the parameters of porous material, including pore distribution, pore capacity and pore density can be easily and precisely controlled by altering the internal and external phase volume fraction, the type of stabilizer and other factors. Overall, the porous materials based on HIPEs template possess many advantages, including low cost, high capacity and excellent reversibility showing huge potential in gas adsorption, separation and enrichment, drug delivery and other practical fields. The present review provides the advanced progresses of preparation of HIPEs and applications in functional materials, with sophisticated porous structures and desirable environmental adaptabilities. Initially, we clearly summarize the synthesizing strategies in regard to both corresponding mechanisms and typical examples developed in recent years, including oil-in-water (O/W) HIPEs, water-in-oil (W/O) HIPEs, oil-in-oil (O/O) HIPEs, high internal phase supercritical fluid emulsions, high internal phase ionic liquid emulsion and high internal phase deep eutectic solvent emulsion. Subsequently, we also clearly discuss in detail the selection of stabilizers including traditional surfactants, solid particles, and low molecular weight or macromolecular gelators, and the influence of various external environmental factors on the stability of high internal phase emulsions (the features of phase, temperature and electrolyte). Meanwhile, we further look forward to their potential applications in functional material preparation, including the functional porous materials, flexible wearable devices and stimulus responsive material. Moreover, the limitations of the existing porous functional materials based on high internal phase emulsion are discussed, including inadequately mechanical performance and unsatisfactory biocompatibility, which will provide significant guidance for synthesizing strategies and practical application in the future. In the end, the current challenges and perspectives on the future development of functional HIPEs materials are also discussed.

We recently published an article “Conventional and Microwave Hydrothermal Synthesis and Application of Functional Materials: A Review” on Materials, and we are honored to receive a comment article from Jalouli et al. We will give a detailed explanation for the confusion of the mechanism of crystal nucleation and growth in the comment article.

With the increasing depth of proteomic identification, quantitative accuracy and increasing analytical speed, new challenges are being encountered in the development of proteomics methods. Traditional proteomics methods are time-consuming and have low sensitivity and poor accuracy; hence, they do not satisfy the new demands in proteomics research. Preparation of novel materials with specific functions via chemical and biochemical routes or by methods based on electricity, magnetism, heat, and photoirradiation is the key to overcome the limitations of traditional analytical techniques and promote active research in the field of proteomics. This paper reviews the recent advances in the application of functional materials in proteomics researches.

Cu-boosted one-pot nanoarchitectonics for synthesis of polydopamine membranes as reusable laccase mimic

The charge transfer (CT) interactions of quercetin 3-O-rutinoside (Q3OR) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE) are investigated at CAM-B3LYP /def2-TZVP level in gas and solvent phases (methanol/ethanol). Geometry optimizations, frontier molecular orbital (FMO) analysis, global reactivity descriptors and UV-visible spectra are calculated to elucidate the nature and strength of donor-acceptor interactions. The Q3OR-DDQ complex displayed superior electronic delocalisation, higher dipole moments and a more significant red shift in UV absorption maxima, highlighting stronger CT interactions than Q3OR-TCNE. The in-depth electronic structure analysis via density of states (DOS) and non-covalent interaction (NCI) plots supported enhanced stabilisation of its charge transfer complex. Furthermore, the atoms-in-molecules (AIM), electron localisation function (ELF), localised orbital locator (LOL), electron density difference (EDD) maps and natural bond orbital (NBO) studies revealed an efficient electron transfer process with significant orbital overlap in Q3OR-DDQ in ethanol phase. These findings provide theoretical insights into the electronic properties and molecular interactions of Q3OR with π-acceptors, highlighting the potential of such complexes in functional material and pharmaceutical applications.

The surface plasmon resonance (SPR) of noble metals is known to improve the efficiency of various processes and devices. The photocatalytic process is the production of fuels and storage of solar photons in chemical bonds without imposing harmful threats to the environment. Photovoltaics are other devices utilizing solar energy for electrical energy. Similarly, other optoelectronic devices like photodetectors absorb photons and convert it into charges via electron–hole dissociation processes. In contrast, light‐emitting optoelectronic devices work based on the phenomenon of charge recombination to produce light. All these devices, however, have efficiency limitations, which impede the application of novel functional materials in these devices. A more direct approach is the utilization of noble metals and their complexes, which significantly enhance the efficiencies of these devices by SPR. This article highlights recent works and applications of noble metals by SPR‐enhanced photocatalysis for hydrogen evolution from water, CO2 conversion into useful compounds, and oxidation of hazardous pollutants. In addition, the plasmon‐enhancement of optoelectronic devices is summarized. Several possible mechanisms that have been previously reported in the literature are discussed in this work, with particular emphasis on different features of these mechanisms involving devices that are not highlighted and therefore need more attention.

Nitrogen heterocycles are widespread in nature and their applications in bioactive pharmaceuticals, agrochemicals and functional materials are well known. A number of protocols have been developed for their syntheses. This review article covers an updated (published during 2005-2008) summary of transition metal-catalyzed approaches for the syntheses of five- and six-membered ring heterocycles with one nitrogen atom via carbon-nitrogen bond forming reactions. The syntheses of five-membered ring heterocycles include pyrroles, pyrrolidines, indoles, oxindoles, isoindoles, indolizines and carbazoles. The syntheses of six-membered nitrogen heterocycles covered are pyridines, piperidines, quinolines and isoquinolines. In some cases, mechanistic rationalizations for the formation of the heterocycles have also been discussed.

CHEMISTRY Many of the most useful organic reactions are catalyzed by noble metals, which not only are expensive but also can be hazardous if released into the environment. One example is the Suzuki-Miyaura reaction, in which the cross coupling of an aromatic halide and an arylboronic acid is catalyzed by a Pd(0) complex or supported catalyst. Thathagar et al . explored the use of nanoparticles (typically 1.6 to 2.1 nanometers in diameter) of copper, noble metals (ruthenium, palladium, and platinum), and copper-noble metal alloys. For the simplest example, which produces biphenyl, pure Cu nanoparticles were active and stable catalysts, although the yields and reaction rates were lower than for pure Pd particles. However, a Cu-Pd alloy was actually more active than pure Pd. These results outline a potential compositional space for exploration of alternative catalysts for this reaction. — PDS J. Am. Chem. Soc. 10.1021/ja027716+.