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Here, analytical extended multi-state complete active space second-order perturbation method (XMS-CASPT2) gradients are used to rationalize the decreasing triplet quantum yield trend in 2-nitronaphthalene, 1-nitronaphthalene, and 2-methyl-1-nitronaphthalene, a series of nitro-substituted aromatic compounds. Comparison with the XMS-CASPT2//CASSCF (where CASSCF stands for complete active space self-consistent field method) results highlights the importance of dynamic correlation in geometry optimization and challenges the validity of an XMS-CASPT2//CASSCF approach: XMS-CASPT2 S1 minima leads to planar structures, while CASSCF optimizations trigger a pyramidalization of the nitro group. The XMS-CASPT2 results correlate the reported decreasing triplet quantum yield trend in these species to a decrease in S1 to T2 population transfer and an increase in S1–S0 decay, while no such correlation is observed when using XMS-CASPT2//CASSCF data. [ABSTRACT FROM AUTHOR]

Understanding core level shifts in aromatic compounds is crucial for the correct interpretation of x-ray photoelectron spectroscopy (XPS) of polycyclic aromatic hydrocarbons (PAHs), including acenes, as well as of styrenic polymers, which are increasingly relevant for the microelectronic industry, among other applications. The effect of delocalization through π aromatic systems on the stabilization of valence molecular orbitals has been widely investigated in the past. However, little has been reported on the impact on the deeper C1s core energy levels. In this work, we use first-principles calculations at the level of many body perturbation theory to compute the C1s binding energies of several aromatic systems. We report a C1s red shift in PAHs and acenes of increasing size, both in the gas phase and in the molecular crystal. C1s red shifts are also calculated for stacked benzene and naphthalene pairs at decreasing intermolecular distances. A C1s red shift is in addition found between oligomers of poly(p-hydroxystyrene) and polystyrene of increasing length, which we attribute to ring–ring interactions between the side-chains. The predicted shifts are larger than common instrumental errors and could, therefore, be detected in XPS experiments. [ABSTRACT FROM AUTHOR]

In this study, the performance of the doubles-corrected higher random-phase approximation [HRPA(D)] has been investigated in calculations of nuclear magnetic resonance spin–spin coupling constants (SSCCs) for 58 molecules with the experimental values used as the reference values. HRPA(D) is an approximation to the second-order polarization propagator approximation (SOPPA) and is, therefore, computationally less expensive than SOPPA. HRPA(D) performs comparable and sometimes even better than SOPPA, and therefore, when calculating SSCCs, it should be considered as an alternative to SOPPA. Furthermore, it was investigated whether a coupled-cluster singles, doubles and perturbative triples [CCSD(T)] or Møller-Plesset second order (MP2) geometry optimization was optimal for a SOPPA and a HRPA(D) SSCC calculation for eight smaller molecules. CCSD(T) is the optimal geometry optimization for the SOPPA calculation, and MP2 was optimal for HRPA(D) SSCC calculations. [ABSTRACT FROM AUTHOR]

Selective activation of the C–H bond of aromatic hydrocarbons is significant in synthetic chemistry. However, achieving oriented C–H activation remains challenging due to the poor selectivity of aromatic C–H bonds. Herein, we successfully constructed alternately arranged Au–C4 and Au–O4 organometallic coordination networks through selective aromatic C–H bond activation on Au(111) substrate. The stepwise reaction process of the 5, 12-dibromopyrene 3,4,9, 10-tetracarboxylic dianhydride precursor is monitored by high-resolution scanning tunneling microscopy. Our results show that the gold atoms in C–Au–C organometallic chains play a crucial role in promoting the selective ortho C–H bonds activation and forming Au–C4 coordination structure, which is further demonstrated by a comparative experiment of PTCDA precursor on Au(111). Furthermore, our experiment of 2Br-PTCDA precursor on Cu(111) substrate confirms that copper atoms in C–Cu–C organometallic chains can also assist the formation of Cu–C4 coordination structure. Our results reveal the vital effect of organometallic coordination on selective C–H bond activation of reactants, which holds promising implications for controllable on-surface synthesis. [ABSTRACT FROM AUTHOR]

Chiral macrocyclic arenes possess confined three-dimensional asymmetric cavities, electron-rich structures, chiral luminescence properties and excellent enantioselective recognition properties and have become a frontier and hotspot of macrocyclic chemistry and supramolecular chemistry. In recent years, there has been growing interest in the development of novel chiral macrocyclic arenes, which have found applications in various research areas. In this review, the construction, properties and functional applications of novel chiral macrocyclic arenes in enantioselective recognition, chiral sorting and construction of chiral luminescent materials according to their chiral types, including central, axial, planar, and inherent chiralities, are summarized. It is expected that this review will be helpful for research on supramolecular chemistry and for promoting the development of synthetic chemistry, materials chemistry and biochemistry. [ABSTRACT FROM AUTHOR]

The reaction of γ-stannylated propargyl esters in the presence of a cationic gold(I) catalyst affords vinylidenecyclopropane derivatives as a mixture of diastereomers. The cis-geometry of the alkenes is almost entirely retained in the product. DFT calculations suggest the involvement of the gold(I)-stabilized propargyl cation as a resonance form of gold(I)-coordinated allenylidene species. [ABSTRACT FROM AUTHOR]

Developing efficient photocatalysts is one of green and low cost tactic for addressing the environmental deterioration and energy crisis. Therefore, it remains a fantastic and important strategy to design an efficient junction between different semiconductors for harvesting solar light, boosting the redox capability. Herein, the fabrication of ZnS in situ decorated CdIn 2 S 4 (referred to as CIS-Zx) were prepared by converting ZnS particles on Cd 2 In 4 S surface by a facile cation exchange method during solvothermal synthesis. According to a series of PEC measurements and DFT calculations, the bending of band edge as well as the establishing of built-in electric field in the interface of CIS/ZnS heterojunction were concluded, causing the formation of in-situ S-scheme heterojunctions in CdIn 2 S 4 /ZnS. The in-situ S-scheme heterojunctions can effectively ameliorate the migration behaviors of photo-generated charges. Compared with pure CdInS 4 , ZnS and physically mixed CdIn 2 S 4 /ZnS, the CIS-Zx in-situ S-scheme heterojunction exhibits efficient photocatalytic activity and stability in the selective reduction of aromatic nitro compounds and oxidation of aromatic alcohols, it is hoped that this work will open up a new avenue for innovative applications of in-situ S-scheme heterojunctions. [Display omitted] • An in-situ heterojunction was fabricated by a cation exchange method. • The S-scheme mechanism was certified by DFT calculation and PEC characterization. • Such in-situ S-scheme heterojunction shows significantly improved selective redox abilities. [ABSTRACT FROM AUTHOR]

A catalytic metal‐free approach for the H/D exchange in aromatic compounds using D2O as the terminal deuterating reagent has been developed. This metal‐free protocol employs a triaryl carbenium as the mediator and showcases a wide applicability in the late‐stage deuteration of various natural products and small‐molecule drugs. Gram‐scale deuteration was successfully demonstrated with β‐Estradiol, highlighting the method's practicability. Detailed mechanistic insights, supported by DFT calculations, unveiled the essential role of in situ generated acidic species in this electrophilic aromatic substitution process. This newly developed method offers a sustainable and versatile alternative to traditional metal‐catalyzed H/D exchange techniques, addressing challenges such as the use of expensive metals, impurity formation, and the necessity for residual metal removal from the final products. [ABSTRACT FROM AUTHOR]

With only a handful of compounds known, opportunities to explore the structure and reactivity of dialumenes and related dialumene adducts have been limited. For the first time, a series of dialumene-arene adducts have been synthesised; adduct formation has been probed experimentally and through DFT, and their reactivity investigated. [ABSTRACT FROM AUTHOR]

Unlike most attempts to find compounds with activity against SARS-CoV-2 aimed at reusing approved drugs, our goal was to find compounds with antiviral activity among the 1,2-dithioloquinoline derivatives we synthesized. These compounds exhibit pleiotropic effects, having a novel structure compared to known pharmaceuticals. In this work, we diversified the structure of 1,2-dithioloquinoline by introducing various substituents (chlorine atom, ether, amide, sulfonamide groups, pharmacophore heterocycles) into different positions of this tricyclic framework. Using docking with further quantum chemical post-processing of calculations of the created virtual library of 404 structures, more than ten compounds of the aryl(4,4-dimethyl-4,5-dihydro-1H-[1,2]dithiolo[3,4-c]quinoline-1-ylidene)amine series were discovered, synthesized and experimentally studied. The bioactive screening of newly synthesized compounds revealed that six of them demonstrate suppression of SARS-CoV-2 replication in Vero E6 cell culture in the micromolar range of EC50 values (from 0.27 to 98.48 μM). The best compound, in the structure of which fragments of tricyclic dithioloquinoline and streptocide are combined, demonstrated a highest ability to protect Vero E6 cells from SARS-CoV-2 with EC50 = 0.27 μM, as well as low cytotoxicity with a selectivity index SI > 370, exceeding all reference values compounds used in the study (remdesivir, GC376, ML188). [ABSTRACT FROM AUTHOR]

ABSTRACT Rose (Rosa rugosa) is an important perfume plant, but its cultivation is significantly constrained by salt stress. Terpenes represent the most abundant volatile aromatic compounds in roses, yet little is known about how terpene metabolism responds to salt stress. In this study, salt‐treated rose petals presented significant accumulation of monoterpenes, including geraniol, due to the disruption of jasmonic acid (JA) biosynthesis and signalling. Overexpression and silencing analyses revealed a MYC transcription factor involved in JA signalling (RrbHLH105) as a repressor of geraniol biosynthesis. RrbHLH105 was shown to activate the trehalose‐6‐phosphate synthase genes RrTPS5 and RrTPS8 by binding to the E‐box (5′‐CANNTG‐3′). The increased trehalose‐6‐phosphate content and decreased geraniol content in rose petals overexpressing TPS5 or RrTPS8, along with the high accumulation of geraniol in petals where both RrbHLH105 and TPSs were cosilenced, indicate that trehalose signalling plays a role in the negative regulation of geraniol accumulation via the RrbHLH105‐TPS module. In summary, the suppression of RrbHLH105 by salt stress leads to excessive geraniol accumulation through the inhibition of both RrbHLH105‐mediated JA signalling and RrTPS‐mediated trehalose signalling in rose petals. Additionally, this study highlights the emerging role of RrbHLH105 as a critical integrator of JA and trehalose signalling crosstalk. [ABSTRACT FROM AUTHOR]

Inherently chiral calixarenes hold great potential for applications in chiral recognition, sensing, and asymmetric catalysis due to their unique structures. However, due to their special structures and relatively large sizes, the catalytic asymmetric synthesis of inherently chiral calixarenes is challenging with very limited examples available. Here, we present an efficient method for the enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes through the desymmetrizing electrophilic sulfenylation of calix[4]arenes. This catalytic asymmetric reaction is enabled by a chiral 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst and hexafluoroisopropanol. Various inherently chiral sulfur-containing calix[4]arenes are obtained in moderate to excellent yields with high enantioselectivities. Control experiments indicate that the thermodynamically favored C-SAr product is formed from the kinetically favored N-SAr product and the combination of the chiral sulfide catalyst and hexafluoroisopropanol is crucially important for both enantioselectivity and reactivity. Due to the special structures and relatively large sizes, the catalytic asymmetric synthesis of inherently chiral calixarenes is challenging with limited examples available. Here, the authors report the enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes through the desymmetrizing electrophilic sulfenylation of calix[4]arenes. [ABSTRACT FROM AUTHOR]

To explore the inhibiting effect of ionic liquids (ILs) on coal spontaneous combustion (CSC), the long-flame coal was treated by [BMIM][BF4], [BMIM][NO3], [BMIM][I], [EMIM][BF4], and [BMIM][AcO], the thermogravimetric analyzer and FTIR spectrometer were adopted, and they were used to analyze functional groups and mass loss properties of each sample. The combustion and thermokinetic characteristics were obtained at four heating rates, and the relation between each functional group and apparent activation energy was received. The results indicated that, the content of -OH, -CO-O-, -COO-, and aromatic hydrocarbon -CH in ILs-treated coals reduced conspicuously, and the content of C-O and aromatic ring C=C enhanced. Meanwhile, the mass maximum temperature and ignition temperature for ILs-treated coals was delayed, their reaction capacity was weakened markedly. In addition, their apparent activation energy enhanced, in which [BMIM][BF4] showed a higher apparent activation energy. The active group for -COO-, aromatic hydrocarbon -CH, and hydroxyls were main parameters affecting the CSC characteristics by Pearson correlation coefficient method. Those findings guidance for the efficient application of ILs on field of CSC. [ABSTRACT FROM AUTHOR]

Spices played crucial and variable roles in traditions, culture, history, religious ceremonials and festivals along with fetching food flavor and microbial protection globally due to presence of structurally unique and multi-natured chemotypes. Their existence in dishes portrayed key roles in improving shelf life by regulating spoilage of cuisine with different synergistic mechanism. Histo-anatomically (A) sowa exhibited distinguished cellular attributes which created remarkable differences with T. ammi. HPTLC chemometrics of both fruits revealed several peaks for active metabolomics with unique isocratic combination of menstruum. GC-MS study of hydro-distillate exhibited presence of monoterpenic cyclic and aromatic hydrocarbons, alcoholic and ketonic groups along with phenolic derivative that covers majorly 90% of total metabolites. Combined essential oils (EOs 1 + 2) of both fruits showed excellent antimicrobial activity against various clinical pathogenic strains such as K. pneumoniae at 10 µL/mL, S. aureus at 2.5 µL/mL, E. coli and E. faecalis at 1.25 µL/mL, and MRSA and Bcereus at 0.625 µL/mL and (C) albicans at 0.312 µL/mL as the MIC. The antioxidant study of (EOs 1 + 2) with maximum inhibition percentage to DPPH assay was 84.02 ± 1.05 at 100 µg/mL, and minimal inhibition was 72.31 ± 0.63 at 5 µg/mL with IC50 value 4.69 ± 0.22 µg/mL, while ABTS assay extreme was 79.15 ± 2.14 µg/mL and minimal was 67 ± 1.34 with the IC50 value of 18.37 ± 0.15 µg/mL, in superoxide assay uppermost inhibition was 81.03 ± 0.27 µg/mL and lowest was at 65.16 ± 3.15 with the IC50 value 16.46 ± 0.54, and H2O2 radical scavenging activity, predominant value was 78.01 ± 0.47 and least was 64.1 ± 2.01 with IC50 15.58 ± 0.34. These comparative key diagnostic features and synergistic effect of multicomponent natural antimicrobials will provide profound intellect of ancient utility and further scientists to explore their multiple mechanistic modality and application in food and beverages industry. [ABSTRACT FROM AUTHOR]

Inherently chiral calix[4]arenes represent a unique type of chiral molecules with significant applications, yet their catalytic enantioselective synthesis remains largely underexplored. We report herein the catalytic enantioselective synthesis of inherently chiral calix[4]arenes through the sequential organocatalyzed enantioselective Povarov reaction and aromatizations. The chiral phosphoric acid catalyzed three‐component Povarov reaction involving amino group‐substituted calix[4]arenes, aldehydes and (di)enamides desymmetrized the prochiral calix[4]arene substrates, which was followed by various aromatization methods, resulting in a diverse array of novel quinoline‐containing calix[4]arenes with good yields and high enantioselectivities (up to 75 % yield, 99 % ee). The large‐scale enantioselective synthesis and diverse derivatizations of the chiral calix[4]arene products highlight the value of this method. Furthermore, preliminary exploration into their photophysical and chiroptical properties demonstrate the potential applications of these novel calix[4]arene molecules. [ABSTRACT FROM AUTHOR]

We describe the use of acyl imidazoles derived from aliphatic carboxylic acids for the N-heterocyclic carbene/organic photoredox co-catalyzed meta -selective functionalization of electron-rich arenes. Compared to our previous work, a change of the wavelength of the applied LED light from 440 nm to 390 nm promotes this reaction efficiently. [ABSTRACT FROM AUTHOR]

Microbial fermentation has provided fermented foods and important chemicals such as antibiotics, amino acids, and vitamins. Metabolic engineering of synthetic microbes has expanded the range of compounds produced by fermentation. Petroleum-derived aromatic compounds are widely used in industry as raw materials for pharmaceuticals, dyes, and polymers and are in great demand. This review highlights the current efforts in the microbial production of various aromatic chemicals such as aromatic amines, cinnamic acid derivatives, and flavoring aromatics, including their biosynthesis pathways. In addition, the unique biosynthetic mechanism of pyrazine, a heterocyclic compound, from amino acids is described to expand the use of biomass-derived aromatic compounds. I also discuss our efforts to develop high-performance bioplastics superior to petroleum plastics from the aromatic compounds produced by microbial fermentation. [ABSTRACT FROM AUTHOR]

In this work, the degradation of mono‐ and polyfluorinated phenolic compounds was demonstrated by a series of crude plant peroxidases, including horseradish root (HRP) and six members of the Cucurbita genus. Highly active samples were identified using a library screening approach in which more than 50 crude plant samples were initially evaluated for defluorination activity toward 4‐fluorophenol. The highest concentrations were observed in the HRP, pumpkin skin (PKS), and butternut squash skin (BNS), which consistently gave the highest intrinsic rates of decomposition for all the substrates tested. Although HRP exhibited a significant decrease in activity with increased fluorination of the phenolic substrate, PKS showed only minor reductions. Furthermore, in silico studies indicated that the active site of HRP poorly accommodates the steric bulk of additional fluorines, causing the substrate to dock farther from the catalytic heme and thus slowing the catalysis rate. We propose that the PKS active site might be larger, allowing closer access to the perfluorinated substrate, and therefore maintaining higher activity compared to the HRP enzyme. However, detailed kinetic characterization studies of the peroxidases are recommended. Conclusively, the high catalytic activity of PKS and its high yield per gram of tissue make it an excellent candidate for developing environmentally friendly biocatalytic methods for degrading fluorinated aromatics. Finally, the success of the library approach in identifying highly active samples for polyfluorinated aromatic compound (PFAC) degradation suggests the method may find utility in the quest for other advanced catalysts for PFAS degradation. [ABSTRACT FROM AUTHOR]

Viral infectious diseases are spread worldwide. Search for natural antiviral therapy from natural resources to overcome the serious drawbacks of synthetic chemicals is imperative. The antiviral activity against influenza virus subtype H9N2, Herpes simplex II (HSV II), Adenovirus (AdVs), and Newcastle virus (NDV) was assessed using the cytopathic effect (CPE) inhibition assay. Phytochemical investigation of Eriocephalus africanus var. africanus aerial parts led to the isolation and identification of bioactive compounds including a mixture of aromatic hydrocarbons 1 , 3 β -friedelinol 2 , eicosanol 3 , 1-hexadecanol 4 , β -sitosterol 5 , undecanol 6 , pectolinarigenin 7 , cirsilineol 8 , chrysoeriol 9 , kaempferol 10 , tricin 11 , luteolin 12 , 2,4- dihydroxyacetophenone 13 , ferulic acid 14 , β -sitosterol glucoside 15 , afzelin 16 , hesperidin 17 , kaempferitrin 18 , d-(+)–pinitol 19 and 1,5–dimethyl citrate 20. The antiviral assessment revealed promising activity for the total extract against H9N2, HSV II, NDV, and AdVs with selectivity index (SI) = 12.4, 20.8, 27.4, and 12.9, respectively. The Petroleum ether fraction (PE) had promising anti-H9N2, NDV and the adenovirus with SI = 12.1, 17.0, and 19.1, respectively. Molecular modeling study proved promising activity for β -sitosterol with H9N2 (ΔG = -7.17 Kcal/mol), kaempferitrin with HSV-II (ΔG = -7.64 Kcal/mol), 3 β -friedelinol with AdVs (ΔG = -7.63 kcal/mol), and pectolinarigenin with NDV (ΔG = -7.55 Kcal/mol.). The top 4 candidates showed promising druglikeness and drug-score with no potential toxicity except for pectolinarigenin and kaempferitrin. They showed low to high probability for intestinal absorption, no BBB permeation with zero PAINS alerts and ease for synthetic accessibility. This may establish the promising potential of such compounds for further development into clinical candidates. [Display omitted] • Chromatographic isolation and spectroscopic identification of the bioactive compounds from the aerial parts of Eriocephalus africanus var. africanus cultivated in Egypt. • In silico and in vitro antiviral activity for Eriocephalus africanus total methanol extract as well as other solvent fractions together with the previously isolated essential oil against influenza a virus subtype H9N2, Herpes simplex II, Adeno virus and Newcastle virus. • Estimation of ADME/Tox for isolated compounds. [ABSTRACT FROM AUTHOR]

Acenes or polyacenes are a group of organic compounds and polycyclic aromatic hydrocarbons consisting of benzene ( C 6 H 6) rings that are linearly fused. They are also the building blocks of nanotubes and graphene and follow the general molecular formula C 4 n + 2 H 2 n + 4 . Due to the applications of polyacenes in optoelectronics, they are interesting for chemical and electrical engineering researchers. In this article, the general formulas for distance-based topological indices of Szeged, Mostar, and Padmakar-Ivan are determined by SMP-polynomials, which do not require edge counting and this formula work only by having the number of benzene rings in the composition of polyacenes. [ABSTRACT FROM AUTHOR]

Functionalized 1,2,4,5-tetrasubstituted benzenes are synthetically difficult or laborious to access. The Rh-catalyzed [2+2+2] cycloaddition of a diyne and internal alkyne offers a seemingly straightforward route to these scaffolds; however, this has been largely restricted to alkynes bearing activating (coordinating) functional groups, with very few examples of unactivated alkynes. In this work, we disclose an assessment of Rh-catalyzed [2+2+2] cycloadditions employing unactivated internal alkynes, focusing on the structural diversity and compatibility of both alkyne and diyne components. The limitations of this method are disclosed, with exceptionally bulky alkynes and specific functional groups undergoing side reactions. Furthermore, the practicalities of gram-scale reactions and catalyst recovery/reuse are demonstrated. [ABSTRACT FROM AUTHOR]

The flowers of selected Camellia yuhsienensis Hu specimens were studied at different stages of flowering to determine the volatile components of floral fragrance and how their concentrations changed during efflorescence. The mechanism of fragrance formation and release was also studied in order to provide a theoretical basis for the practical use of C. yuhsienensis Hu flowers. Headspace solid‐phase microextraction (HS‐SPME) was used to extract the natural floral volatile oils of C. yuhsienensis Hu at the different stages, and the floral fragrance components were analysed by gas chromatography–mass spectrometry (GC–MS). A total of 31, 59 and 55 compounds were detected at the budding, early‐blooming and full‐blooming stages respectively. These floral fragrance components included terpene alcohols, as well as other aromatic and aliphatic compounds, and the relative concentrations of the various compounds at different stages of flowering, were different, and those of fatty alcohols and terpene alcohols having higher relative contents at all stages. The main component at the budding stage of C. yuhsienensis Hu was ocimene, which has a grassy fragrance, accompanied by the scent of neroli oil, which gives it a refreshing, gentle and sweet, and explains why the floral fragrance of C. yuhsienensis Hu at the budding stage is extremely thin: the main component during the early‐blooming stage was 3‐carene. A higher percentage of 3‐carene increased the sweetness of the scent, manifesting the typical fragrant characteristics of C. yuhsienensis Hu. The main identified compound at the full‐blooming stage was α‐farnesene, which has a delicate fragrance, accompanied by a balsamic aroma, similar to the scent of gardenia, which is consistent with the sensory characteristics of C. yuhsienensis Hu. [ABSTRACT FROM AUTHOR]

BACKGROUND: Truffle cultivation is evolving rapidly and new agronomic practices such as 'truffle nests' (localized peat amendments of the orchard soil) are being developed. Truffle nests improve the shape of truffles and their depth in the soil and reduce the occurrence of insect damage but have also raised concerns about their impact on the ripeness and maturity of the harvested truffles. In this study, the effect of the nests on the volatile organic compounds profile and the aromatic profile of black truffles was evaluated, as well as the existence of perceptible sensorial differences in truffles. For this, truffles growing in nests were compared with truffles growing in the bulk soil of the same host tree. RESULTS: Gas chromatography showed that nest truffles had a less complex volatile organic compound profile than bulk‐soil truffles. Olfactometry indicated that nest truffles were associated with higher modified frequency values of odorants corresponding to sulfur‐containing compounds. Despite this, sensory evaluation with consumers could not clearly show that nest truffles can be distinguished sensorially from bulk‐soil truffles. CONCLUSION: The results prove that soil conditions can influence the aromatic profile of truffles and thus suggest the possibility of managing truffle aroma using agronomic practices. © 2024 The Author(s). Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

A metal‐free one‐pot synthesis route has been documented for the production of 1,1‐unsymmetrical di‐aryl alkanes via reductive Friedel−Crafts alkylation of arenes with carbonyl compounds in 1,1,1,3,3,3,–hexafluoroisopropanol (HFIP) solvent. This approach exhibits a wide substrate scope accommodating diverse functionalities. The transformation of carbonyl compounds into alkylated products is facilitated by dimethylchlorosilane (Me2SiClH) reduction, succeeded via nucleophilic attack of arenes. The established protocol demonstrates a promising strategy for converting indoline‐2,3‐dione into α‐aryl oxindoles with high yields. The reaction involves reduction with Me2SiClH, followed by the attack of arenes in the presence of a TfOH catalyst. The devised protocol offers scalability and remarkable tolerance towards various functional groups. Control experiments provide insights into the reaction mechanism, highlighting the crucial roles of HFIP and Me2SiClH. Furthermore, the method is adaptable for late‐stage functionalization of numerous natural products and pharmaceuticals such as Sesamol, Thymol, Paracetamol, Menthol, and Nerol. Significantly, the technique has proven effective in efficiently synthesising the anticoagulant drug Phenprocoumon and the rodent control agent Coumatetralyl. [ABSTRACT FROM AUTHOR]

The soju (Korean traditional distilled liquor) market is increasing worldwide. However, in contrast to well-explored distilled liquors, including baijiu (China) and shochu (Japan), soju is less investigated, with limited research on its aroma characteristics. To facilitate better understanding of the aroma characteristics of soju, this study aims to overview recent research on the flavor characteristics of soju and compare data with those of baijiu and shochu, well-established products in the market. Soju is generally made using rice and nuruk (a traditional Korean fermentation starter). Previous studies have reflected that the aroma characteristics vary with raw materials' nutrition percentages, microbial taxa influenced in fermentation starters, and/or pressure reduction during distillation. The research on the aroma characteristics of baijiu, characterized by solid-state fermentation involving qu (a traditional Chinese fermentation starter), is focused on differences in regional characteristics of the flavor type. Research on the aroma characteristics of shochu has primarily demonstrated that the microbial community could contribute significantly to the development of specific aromatic compounds and/or attributes. Moreover, the association of the aroma characteristics of baijiu and shochu with their volatile compound development by the determination of selective ingredients has been examined. Understanding the current research progress can potentially facilitate the improvement in the aroma characteristics of soju. [ABSTRACT FROM AUTHOR]

BACKGROUND: Chemical pollutants, such as nitroaromatic compounds, have been a significant challenge in recent decades of human societies as they contribute to environmental pollution and pose serious health risks due to their high toxicity. One promising and green method to address this issue is the photocatalytic reduction of nitroaromatic compounds to their corresponding amino aromatic compounds. In this study, an rGO/CuBi2O4 nanocomposite was synthesized using the hydrothermal method, involving the simultaneous reduction of graphene oxide and the coupling of CuBi2O4 nanoparticles in its layers. The resulting heterogeneous structure was characterized using various techniques including FTIR, Raman, XPS, XRD, FESEM, TEM, EDAX, UV–Vis DRS, BET, PL spectroscopy, and EIS. Subsequently, the photocatalytic efficiency of the nanocomposite in reducing nitroaromatic compounds to the corresponding aromatic amines under visible light was evaluated. RESULTS: The results indicated that graphene oxide was effectively reduced and coupled with CuBi2O4 nanoparticles in the reduced graphene oxide sheets. The rGO/CuBi2O4 heterogeneous nanocomposite successfully reduced nitroaromatic compounds to the corresponding aromatic amines under visible light. Hydrazine monohydrate was used to supply the necessary hydrogen for the reaction. CONCLUSION: This study confirmed the high photocatalytic activity of the rGO/CuBi2O4 heterogeneous nanocomposite. Our nanocomposite was more effective than others, reported in similar studies, at reducing nitroaromatic compounds to the corresponding amino aromatic compounds. Additionally, it demonstrated high recycling and reuse properties, as there was no significant change in reaction conversion percentage and nanocomposite amount after 16 reuses. © 2024 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) are promising solvents for separating aromatics from fuel oils. However, studies for separate polycyclic aromatics with ILs are rare and insufficient, and the impact of solute structure on extraction performance still needs to be determined. In this work, we use 1‐ethyl‐3‐methylimidazolium bis([trifluoromethyl]sulfonyl)imide ([EMIM][NTF2]) as an extractant to separate 1‐methylnaphthalene, quinoline, and benzothiophene from dodecane mixtures. Liquid–liquid equilibrium experiments identified the optimal operating conditions. Nine solute molecules, including five alkanes and four aromatic hydrocarbons, were used to study the relationship between extraction performance and solute structure. Molecular dynamics simulation and quantum chemistry calculations gave a deep insight and reasonable interpretation of the structure‐performance relationship at the molecular level. An industrial‐scale extraction process was proposed. The IL can be easily regenerated using heptane as a back‐extractive solvent. A high‐purity fuel oil with aromatic content below 0.5 wt% is obtained after 8‐stage extraction. [ABSTRACT FROM AUTHOR]

This study is focused on examining the incorporation of oxidative dehydrogenation into the aromatization of ethane, utilizing thermodynamic analysis and catalytic experiments. The catalysts were characterized by inverse temperature programmed reduction, X‐ray photoelectron spectroscopy (XPS) and X‐ray diffraction (XRD). The results indicated that a blend of the M1 catalyst, containing oxides of vanadium, niobium, and tellurium, with H‐ZSM‐5, serves as an effective catalyst system for the oxidative aromatization of ethane at T = 380 °C. The M1's role in the oxidative dehydrogenation of ethane contributes to de‐bottlenecking the essential step of the reaction. On the zeolitic catalyst aromatic compounds are formed from a surface hydrocarbon pool. In parallel, the oxidation of these intermediates was observed. Also, the formation of paraffins through H‐transfer was evident from the catalytic results. Although the zeolite underwent significant deactivation due to coking, the M1 catalyst demonstrated highly stable activity. Interestingly, the system did not show any synergistic effects. Based on the structure‐activity relation of the catalytic system a reaction mechanism is proposed. [ABSTRACT FROM AUTHOR]

Half‐sandwich Ru(II)‐ and Os(II)‐arene complexes have great potential for catalytic and biological applications. The possibility of fine‐tuning their chemical reactivity by including modifications in the ligands around the metal adds to their many advantages. However, structural modifications at the η6‐bound arene have had significant synthetic limitations, particularly in the design of Os(II)‐tethered complexes. For the first time, we have employed a practical C(sp3)‐C(sp2) coupling to obtain 28 new Ru(II) and Os(II) η6‐arene half‐sandwich complexes with a wide variety of arene functionalities, including those that enable the formation of tether rings, such as quinoline, and coumarin. The introduction of novel functional groups at the arene in Ru(II)‐ and Os(II) half‐sandwich complexes can broaden the synthetic scope of this type of organometallic complexes, and help to take full advantage of their structural diversity, for example, in intracellular catalysis. [ABSTRACT FROM AUTHOR]

An efficient Pd-catalyzed asymmetric hydroesterification of vinyl arenes on water is reported. A variety of phenyl 2-arylpropanoates can be obtained in good yields with high b/l ratios and ee's with phenyl formate or CO as a carbonyl source. (R)-DTBM-SEGPHOS was found to be an effective ligand for the reaction under aqueous conditions. The hydrophobicity of the ligand appeared to be crucial to the hydroesterification reaction, which likely proceeded "on water". [ABSTRACT FROM AUTHOR]

Supercritical water (SCW) gasification technology can enable the efficient utilization of coal by converting it to hydrogen-rich gas. However, poly-cyclic aromatic hydrocarbons and heavy components, which are intermediates of supercritical water gasification, tend to generate char, hindering the complete gasification of coal. In this work, phenol is recycled to enhance the gasification process and reduce the formation of these intermediates during SCWG, and the regulation mechanism is investigated. The results demonstrate that both gas yield and gasification efficiency increase with the presence of phenol, reaching approximately 98.5% at 750 °C, concentration of 2%with the effect of phenol, which is 27% higher than that in the coal-water system. Organics removal rate reaches about 98% with the addition of phenol. Phenol can enhance the gasification performance by facilitating the conversion of heavy components to lightweight components. The transient reactivity of coal in the poly-condensation stage is increased by about 50 times with the presence of phenol. The regulation mechanism of phenol in the poly-condensation stage during coal gasification involves the decomposition of SCW forming hydroxyl radicals, which replaces the substituents on the benzene ring, facilitating the dissociation of benzene ring into small molecules that are prone to polymerize. The interacting force between phenol and multi-rings disrupts the conjugate structure, aiding in the decomposition of polycyclic organics into small molecules. • Investigated the regulating mechanism of phenol on the gasification process. • Hydrogen yield and gasification efficiency increases with the presence of phenol. • Nearly complete gasification (98.5%) is realized with the presence of phenol. • The organics removal rate reaches about 98% with the presence of phenol. • Reactivity of coal in the polycondensation stage increased by 50 times with phenol. [ABSTRACT FROM AUTHOR]

The dearomatizations of non‐activated arenes, particularly those under mild reaction conditions, are highly desired transformations in organic synthesis due to their power in converting flat aromatic rings into three‐dimensional frameworks. Although hypervalent iodine (HVI)‐mediated dearomatization of phenol derivatives has developed rapidly, HVI‐mediated dearomatization of non‐activated arenes remains an urgent and challenging task. To fulfil this task, in this work, we established an HVI‐mediated oxidative dearomatization of non‐activated arenes by using biphenylureas and N‐ or O‐nucleophiles as reactants. This electrophilic dearomatization (DEAr) process is highly regioselective, which enabled different N‐ and O‐nucleophiles to react at the distal C4‐position of the phenyl ring, thus generating dearomative spiro‐products in a single step under mild conditions with wide substrate scope (43 examples, 22%–76% yield). This approach not only provides a successful example for dearomatization of non‐activated arenes under mild reaction conditions, but also has overcome the challenges in HVI‐mediated dearomatization of non‐activated arenes, which will enrich the chemistry of dearomatization. [ABSTRACT FROM AUTHOR]

Cascade dearomative functionalization is a robust protocol to convert flat arenes into medicinally relevant three‐dimensional architectures with added new functionality. Herein, a dearomative cycloaddition protocol for synthesizing tetrahydroquinoline‐embedded α‐tertiary amine scaffolds has been developed employing quinolinium salts and sulfonyl azides under metal‐free conditions. An underexplored and mechanistically distinct pathway is unveiled, creating quaternary‐center‐bearing amine skeletons by an amine group migration during the transfer hydrogenation and cycloaddition cascade reaction. This approach provided a broad substrate scope of α‐tertiary amine scaffolds from a plethora of C3‐substituted quinolinium and sulfonyl azides. The post‐synthetic modifications have further diversified the α‐tertiary amine core into interesting scaffolds. Preliminary mechanistic studies suggested the involvement of aziridine ring formation for the amine migration to the C‐3 position of quinoline to generate the α‐tertiary amine core. [ABSTRACT FROM AUTHOR]

Dearomative trifluoromethylation of arenes provides an ideal method for constructing CF3‐containing three‐dimensional architectures which are of increasing interest in drug discovery. However, such transformation is rare and challenging because of the inherently low reactivity of arene π‐systems and selectivity issues. Herein, we disclose a general dearomative 1,2‐hydrotrifluoromethylation of (hetero)arenes utilizing activation by temporary π‐complexation to chromium, thus affording convenient access to 1,3‐cyclohexadienes bearing the privileged CF3 group. The versatility of this strategy further enables a dearomative 1,2‐deuterotrifluoromethylation with high deuterated ratios. The related dearomative 1,2‐(deutero)hydroperfluoroethylation reactions were conducted well for a range of chromium‐bound (hetero)arenes. Finally, a reasonable mechanism was proposed based on the intermediate capture and control experiments. [ABSTRACT FROM AUTHOR]

AbstractDifferent coal seams go through distinct biological, physical, and chemical processes. Polycyclic aromatic compounds (PACs) in coal may retain information about these processes, especially in low-rank bituminous coals. Three coal seams with different sulfur contents from the Ningwu Coalfield were studied to understand the relation of different sulfur contents with PAC formation in low-rank bituminous coals. Coal samples were extracted by solvent and separated using liquid chromatography. The collected aromatic hydrocarbon fractions were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). A total of 27 sulfur-containing PACs (SPACs) were identified in the high-sulfur samples, whereas only 8 SPACs were found in the low-sulfur coal and middle-sulfur coal. The total SPACs to total PACs ratios (T-SPACs/T-PACs) are 1.15%, 2.17%, and 10.65% in the low-sulfur, middle-sulfur, and high-sulfur coal, respectively. The variations of SPAC species and their content ratios indicate that SPAC formation is controlled by the sulfur contents in the low-rank bituminous coals. A total of 18 oxygen-containing PACs (OPACs) were identified in the low-sulfur coal and middle-sulfur coal, whereas only 11 OPACs were found in the high-sulfur samples. The average ratios of OPACs to the identified aromatic compounds (T-OPACs/T-PACs) are 9.81%, 9.62%, and 6.91% in the low-, middle-, and high-sulfur coals, exhibiting a negative correlation with sulfur contents and indicating that OPACs were also influenced by sulfur contents in low-rank bituminous coals. The ratios of total contents of polycyclic aromatic hydrocarbons (PAHs) to total PACs (T-PAHs/T-PACs) are 89.1%, 88.2%, and 82.0% in the low-, middle-, and high-sulfur coals, respectively, indicating a decreasing trend from low- and middle-sulfur coal to high-sulfur coal. This variation could be caused by the reaction of PAHs and sulfur to form SPACs. [ABSTRACT FROM AUTHOR]

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Environmental contamination found in urban areas generally has a chemical composition that favors the generation of a variety of physical, chemical and biological processes that differ from natural soil parameters. Thus, understanding natural attenuation processes in tropical environments is still a challenge, as is understanding how biogeochemical processes can influence and modify natural soil characteristics. The study aimed to apply methods that are not commonly used in investigations of contaminated areas, in order to assess the applicability of non-invasive methodology for detailed stratigraphic characterization and biogeochemical changes resulting from contamination by hydrocarbons in a complex hydrogeological environment site. To date, few studies have presented results obtained using non-invasive techniques to understand biochemical processes. The research was based on the interpretation of results obtained by high-resolution physical environment characterization techniques (such as gamma geophysical profiling and electrical conductivity surveys) and chemical analysis of groundwater. The data was interpreted to obtain a detailed characterization of the study area and evidence of the occurrence of natural attenuation of creosote contamination. The results indicated that the combination of geoenvironmental and geophysical methods is an interesting alternative for obtaining data and understanding the mineralogical and stratigraphic variation of the contaminated area. The physical parameters variations obtained by the methods suggested the presence of local geochemical alterations resulting from natural processes of attenuation of contamination by aliphatic and aromatic hydrocarbons in a tropical environment. The natural attenuation processes were confirmed through groundwater samples, biological analysis and metagenomic classification. [ABSTRACT FROM AUTHOR]

Catalytic conversion of CO2 to valuable products is a promising way to reduce anthropogenic CO2 emission. Herein, a strategy for coupling conversion of CO2 and high‐carbon alkane to CO and gasoline is developed, which is a feasible choice for the combination of CO2 recycling and petroleum refining. The CO2 conversion reaches 2.6% under mild condition (270 °C), and the selectivity of gasoline in the cracking products exceeds 70 wt%. Additionally, the introduction of CO2 improves the selectivity of aromatic hydrocarbons and increases the octane number of gasoline. Mechanism studies indicate that synergistic effect between Brønsted acid centers and Ni sites on the Beta zeolite supported Ni (20 wt%) catalyst (20Ni/β) plays the key role in alkane cracking and CO2 reduction. Notably, 13CO2 isotopic experiments show that the hydrogen produced during the aromatization can be captured by CO2, inhibiting undesired hydrogen transfer pathways and enhanced the yield of aromatics, while CO2 is converted into valuable CO. [ABSTRACT FROM AUTHOR]

In contrast to the locked fluxionality of norcaradienes fused by benzene, unexplored less aromatic heterole‐fused norcaradienes, creatively generated by intramolecular hydroarylation of heteroaryl alkynylcyclopropanes, reserve a balancing fluxionality that permits a dearomative [1,5]‐sigmatropic carbon shift of norcaradienes akin to the reduced aromaticity of heterole. This “walk” shift was confirmed by the isolation of a cycloheptatriene species derived from ring‐expansion of a dearomatized alkynylated heterole‐fused norcaradiene. A following ester‐directed ring‐opening rearomatization of these dearomatized heterole‐fused norcaradienes gives the products featuring migratory acylmethyls that are competent for helicenation with the neighboring (hetero) arenes via (formal) dehydrative alkenylation. Such balancing reactivity of heterole‐fused norcaradienes will open up the opportunity for the development of controllable reactions of fused norcaradienes. [ABSTRACT FROM AUTHOR]

The continuous exploration of new analogs of calixarenes and pillararenes unlocks infinite opportunities in supramolecular chemistry and materials. In this work, we introduce a new class of macrocycle, phenyl‐extended resorcin[4]arenes (ExR4), a unique and innovative design that incorporates unsubstituted phenylene moieties into the resorcin[4]arene scaffold. Single‐crystal analysis reveals a chair‐like conformation for per‐methylated ExR4 (Me‐ExR4) and a twisted "Figure‐of‐eight" shaped conformation for per‐hydroxylated ExR4 (OH‐ExR4). Notably, OH‐ExR4 demonstrates exceptional adsorption capability toward I3− ions in an aqueous solution, with a rapid kinetic rate of 1.18×10−2 g ⋅ mg−1 ⋅ min−1. Furthermore, OH‐ExR4 shows excellent recyclability and potential as a stationary phase in column setups. The discovery of ExR4 opens up new avenues for constructing new macrocycles and inspires further research in functional adsorption materials for water pollutant removal. [ABSTRACT FROM AUTHOR]

The modification of molybdenum carbide catalysts by another transition metal has raised an increasing research interest due to the significant improvement of catalyst activity in hydrodeoxygenation of lignin derivatives. At par with the commonly used Co and Ni that add a strong hydrogenation functionality, it was found that the addition of the more oxophilic W restricts ring hydrogenation while allowing the deoxygenation of oxygenated compounds and thus yielding higher selectivity toward the formation of non‐oxygenated aromatic compounds. The coexistence of Mo2C with W2C along with metallic W altered the electronic properties of Mo2C which resulted in an increase of catalyst active site density and facilitated further total eugenol deoxygenation. Propyl‐benzene selectivity of up to 83 % was reached at close to 100 % eugenol conversion. These findings will allow a better overview of the effect of different metal phases of mixed carbides on the catalyst performance and raise the prospect of optimizing catalyst design for a hydrodeoxygenation processing of lignin depolymerization products. [ABSTRACT FROM AUTHOR]

Seed cakes, by-products from the cold press extraction of vegetable oils, are valuable animal feed supplements due to their high content of proteins, carbohydrates, and minerals. However, the presence of anti-nutrients, as well as the rancidification and development of aflatoxins, can impede their intended use, requiring alternative treatment and valorisation methods. Thermal treatment as a procedure for the conversion of seed cakes from walnuts, hemp, pumpkin, flax, and sunflower into valuable products or energy has been investigated in this paper. Thermogravimetry shows the particular behaviour of seed cakes, with several degradation stages at around 230–280 and 340–390 °C, before and after the typical degradation of cellulose. These are related to the volatilisation of fatty acids, which are either free or bonded as triglycerides, and with the thermal degradation of proteins. Torrefaction at 250 °C produced ~75–82 wt% solids, with high calorific values of 24–26 kJ/g and an energy yield above 90%. The liquid products have a complex composition, with most parts of the compounds partitioning between the aqueous phase (strongly dominant) and the oily one (present in traces). The structural components of seed cakes (hemicelluloses, cellulose, and lignin) produce acetic acid, hydroxy ketones, furans, and phenols. In addition to these, most compounds are nitrogen-containing aromatic compounds from the degradation of protein components, which are highly present in seed cakes. [ABSTRACT FROM AUTHOR]

After several years of gas production, a black solid hydrocarbon material began to be produced along with the gas stream from the Risha gas field, in the northeastern part of Jordan. The main reason for the formation of this material is still unknown until this time, so knowing the source of this material is this study's main goal. Organic geochemical studies for black solid material and effective source rocks (Lower Silurian shales) are used to determine the physical and organic components of the produced black solid material (heavy oil) and attempt to identify its source. The black solid material demonstrates high organic carbon (TOC = 12% by leco instrument) and a high calorific value, like those of oils, asphalts, and shale oils with moderate sulfur content. The gross composition of the black solid material sample is dominated by saturates and asphaltene but contains very low aromatic hydrocarbons reflecting the naphthenic oil type. Meanwhile, the Silurian extracts range between paraffinic and paraffinic-naphthenic organic matters. The biomarker indicators related depositional environment and carbon isotopic composition for the black solid material sample and Silurian extracts, show that they were relatively deposited in a reducing marine environment. The black material reveals lower maturity level than the Silurian extracts. Oil/source rock correlation study for the studied samples suggests strong affinity between the black material and Lower Silurian source rock in their source characteristics, suggesting that the black hydrocarbon material was expelled from the Silurian source rocks at low maturity stage as normal oil. This normal oil is subjected to secondary alteration process (evaporative fractionation) and was stored in the reservoir. It contaminated with some inorganic material that was introduced into the well as a component of a drilling mud additive or drill string lubricant or, potentially, in part, a corrosion product of wellbore tubulars, since significant iron was present in the sample. [ABSTRACT FROM AUTHOR]

A company's 3.1 MM TPY continuous reforming unit adopts domestic ultra-low pressure continuous reforming (SLCR) technology with indigenous intellectual property, and uses continuous reforming catalyst PS-VI. It is currently the largest domestic continuous reforming unit. During the shrink-fit assessment stage after the large-scale installation, the displacement of various equipment and pipeline supports and hangers in the reaction and regeneration system is normal and consistent with the design data. After the unit is put into operation, the trend of thermal displacement in the reaction and regeneration system is consistent with the results of the shrink-fit assessment. The performance assessment results of the unit show that, in the case where the aromatic potential content of the raw material is 7.49 percentage points lower than the design value, the liquid yield of C5+ of the unit is 88.15%, the pure hydrogen yield is 3.80%, the mass fraction of aromatic hydrocarbon in the depentane oil is 82.84%, and the aromatic hydrocarbon conversion rate is 172% . After half a year of operation, the catalyst dust content remains stable from 8 kg/d to 12 kg/d, and all economic indicators are good. The PS-VI catalyst exhibits good reaction activity, selectivity and low wear rate. [ABSTRACT FROM AUTHOR]

Aromatic substitution of redox‐active aromatic compounds could be initiated by a preceding redox step. We report on the different reaction pathways of such redox‐induced substitution (RIAS) reactions between a redox‐active guanidino‐functionalized aromatic molecule (GFA) and an amine or guanidine. Oxidation of the GFA leads to an umpolung of the guanidine from a nucleophile to an electrophile and thereby enables addition of the amine or guanidine. Several examples are given, demonstrating the use of redox substitution in synthetic chemistry, e. g. for the convenient synthesis of novel N‐heteropolycyclic molecules and unsymmetrically‐substituted aromatics. [ABSTRACT FROM AUTHOR]

Herein, we report visible-light induced C–O bond cleavage of vinyl-appended cyclic synthons via a Co(II)-photoredox dual catalytic approach operating at room temperature. This methodology exhibits a broad scope and is capable of accessing linear as well as branched allyl arenes simply by tuning the ring size of the cyclic motifs, in a mild and environmentally friendly protocol. Mechanistic studies unveil an interesting aspect of the reaction pathway involving a challenging homolytic cleavage of the Co(III)–O bond, 1,5-HAT of an unstable Co(II)-organometallic intermediate, and the key roles of O2 and the photocatalyst. The successful removal of the directing group further adds an important dimension to the methodology. [ABSTRACT FROM AUTHOR]

AbstractNaphthalene and its derivatives are often determined as markers of environmental pollution, although they are also recognized as crucial building blocks in many beneficial compounds. In the course of this study, a range of 1,2-disubstituted naphthalenes bearing nitro, amine, sulfonate, chlorine, and hydroxyl substituents were synthesized and characterized using several spectroscopic techniques, including FT-IR,1H NMR,13C NMR, DEPT-90, DEPT-135, DEPTq, elemental analysis, and high-resolution mass (HRMs). The NMR analysis of the aromatic hydrocarbon moiety in these compounds emphasized the impact of substituent variations on the appearance of 1H and 13C NMR signals. To resolve the issue of overlapping one-dimensional (1D) 1H NMR signals and determine the connectivity of hydrogen and carbon atoms from the aromatic naphtayl ring, we employed a “two-dimensional” experiment, using homonuclear correlation spectroscopy (2D 1H-1H COSY) and heteronuclear single quantum correlation (2D 1H - 13C HSQC) and heteronuclear multiple‐bond correlation spectroscopy (2D 1H - 13C HMBC). This work also investigated the correlation between 1H NMR signals and thin-layer chromatography (TLC) data. X-ray crystallography data validates that the presence of a specific group, not aligned coplanarly with the naphthyl ring, exerts a spatial influence on the manifestation of 1H NMR signals, alongside other electronic effects. This study will offer NMR data, providing insights into the potential applications and analyses of naphthalene derivatives across various theoretical and practical domains. [ABSTRACT FROM AUTHOR]

Contemporary methods for synthesizing thioesters often necessitate expensive catalysts and harsh conditions, making their synthesis from chemical feedstocks challenging. Herein, we report a sustainable metal-, photocatalyst-, and oxidant-free electron donor–acceptor (EDA) mediated synthesis of thioesters via site-selective C–H functionalization using aryl sulfonium salts (acceptor) with potassium thioacid salts (donor) under visible light irradiation. Our approach enables rapid access to thioesters from a wide variety of arenes, including pharmaceutical and agrochemical compounds, as well as a diverse range of alkyl, aryl, and heteroaryl potassium thioacid salts with excellent efficiency and regioselectivity. Mechanistic studies supported the formation of an EDA-complex, and radical trapping experiments corroborated the involvement of a radical-based mechanism for the product formation. Moreover, our method demonstrates excellent atom economy and E-factor scores, which are considered excellent in terms of safety, economic and ecological yardsticks. [ABSTRACT FROM AUTHOR]

Inherently chiral calixarenes are known to exhibit versatile functions due to their delicate three-dimensional macrocyclic frameworks. However, the catalytic asymmetric synthesis of these compounds remains largely unexplored and poses a significant challenge. Herein, we report an unprecedented enantioselective electrochemical synthesis of inherently chiral calix[4]arenes. Our approach is based on a 3d metal cobalt-catalyzed asymmetric C–H acyloxylation of the prochiral macrocyclic frameworks. The easily accessible and modifiable chiral salicyloxazoline (Salox) was used as the ligand to efficiently regulate the enantioselectivity. This protocol proceeded smoothly under electrochemically mild conditions and was compatible with a wide range of carboxylic acids, including aryl carboxylic acids and tertiary, secondary, primary aliphatic carboxylic acids, yielding a variety of acyloxylated calix[4]arenes with good yields (up to 94% yield) and excellent enantioselectivities (95–99% ee). The synthetic practicability of this method was demonstrated by the scale-up reaction and the divergent derivatizations of the inherently chiral macrocyclic products. [ABSTRACT FROM AUTHOR]

Metal–metal oxide interface catalysts are in high demand for advanced catalytic applications due to their multi‐component active sites, which facilitate synergistic cooperation where a single component alone cannot effectively promote the desired reaction. Demonstrated herein graphene oxide‐supported nanoscale Mn3O4‐CoO−Co as highly efficient catalysts for hydrogenation of nitro styrenes/nitro arenes to amino styrenes/arenes under mild reaction conditions (0.5 MPa and 100 °C in 1 : 1 THF/water). Charge relocalization at the Co‐CoO‐Mn3O4 heterojunction interfaces, primarily driven by Mn3O4, significantly improves reaction selectivity. Replacing Mn3O4 with MnO or using other supported bimetallic CoMnOx catalysts decreases selectivity, leading to the formation of a mixture of products. The catalyst demonstrated remarkable selectivity in converting nitro groups to amines, even in the presence of highly reactive functional groups such as C=C, O−C=O, C=O, C≡N, chalcones, and halides. It also exhibited high yields, multiple reusability, and a broad substrate scope. This study demonstrates how Mn3O4, in synergy with CoO−Co, fine‐tunes selectivity, paving the way for the development of advanced metal‐metal oxide interface catalysts to enhance both selectivity and efficiency in organic transformations. [ABSTRACT FROM AUTHOR]