Direct Synthesis Research Articles

Direct Introduction of Perfluoroacyl (−CORF) Groups into Organic Substrates

AbstractThe direct addition of perfluoroacyl (−CORF) groups to organic frameworks has seen a resurgence in interest due to the benefits of these groups in late‐stage modification of pro‐drugs and biologically active compounds, helping to identify new active leads. The presence of −CORF groups positively impacts the structure‐activity relationships of these compounds. In that sense, both polar methods and radical protocols have been developed for the direct syntheses of trifluoromethyl and perfluoroalkyl ketones. In particular, methodologies to tame the unstable trifluoroacyl radical, which could be a key intermediate in the late‐stage syntheses of trifluoroacyl‐substituted compounds, has allowed much progress in this area. In the next sections, the direct incorporation of perfluoroacyl groups into (hetero)aromatic compounds, −CORF substitutions at Csp3−H, alkyl halides, alkenes, amides, and N‐atoms will be discussed in detail, suggesting the future directions and perspectives in the field. These known reactions are summarized in Table 1.

Microemulsion Templating Synthesis of Hierarchical Porous Ag‐Doped SiO2‐TiO2 Composites for Efficient Degradation of Noxious Methylene Blue Dye: Effect of Calcination Environment

AbstractWe report herein a dual function mesoporous structure of titanium oxide based porous carbon with large surface‐to‐volume ratios for efficient degradation of noxious methylene blue dye (MB) from an aqueous environment. The mesoporous photocatalysts is fabricated via direct template synthesis of highly ordered silica‐titania monolith doped with Ag0/Ag2O starting from a quaternary microemulsion liquid crystalline phase. The produced monoliths are subjected in‐situ to doping by growing silver, in the cubic cavities, and on the silica/titania structure's domain. This study investigated the efficiency of novel composite materials, consisting of silver‐doped silica‐titania (SiO2/TiO2), which is synthesized using the microemulsion templating approach. The photocatalytic performance of the synthesized composite in the photodegradation of MB has been studied. The procedure of photodegradation was employed to achieve decolorization of the cationic MB dye using visible light. The catalyst effectively achieved the decolorization of the dyed solution through the processes of adsorption and photodegradation. The composite consisting of SiO2, TiO2, and Ag2O at a ratio of 1 : 1:0.5, which underwent calcination in an air environment (AgOST), exhibited a removal efficiency of 99 % compared to its calcined state under argon (AgSTC).

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO2 and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO2 and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO2, the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Metal-Based Oxygen Reduction Electrocatalysts for Efficient Hydrogen Peroxide Production.

Hydrogen peroxide (H2O2) is a high-value chemical widely used in electronics, textiles, paper bleaching, medical disinfection, and wastewater treatment. Traditional production methods, such as the anthraquinone oxidation process and direct synthesis, require high energy consumption, and involve risks from toxic substances and explosions. Researchers are now exploring photochemical, electrochemical, and photoelectrochemical synthesis methods to reduce energy use and pollution. This review focuses on the 2-electron oxygen reduction reaction (2e- ORR) for the electrochemical synthesis of H2O2, and discusses how catalyst active sites influence O2 adsorption. Strategies to enhance H2O2 selectivity by regulating these sites are presented. Catalysts require strong O2 adsorption to initiate reactions and weak *OOH adsorption to promote H2O2 formation. The review also covers advances in single-atom catalysts (SACs), multi-metal-based catalysts, and highlights non-noble metal oxides, especially perovskite oxides, for their versatile structures and potential in 2e- ORR. The potential of localized surface plasmon resonance (LSPR) effects to enhance catalyst performance is also discussed. In conclusion, emphasis is placed on optimizing catalyst structures through theoretical and experimental methods to achieve efficient and selective H2O2 production, aiming for sustainable and commercial applications.

Direct Synthesis of Benzothiazoles and Benzoxazoles from Carboxylic Acids Utilizing (o-CF3PhO)3P as a Coupling Reagent.

A general and efficient method for the direct synthesis of benzothiazoles and benzoxazoles from carboxylic acids with 2-aminobenzenethiols or 2-aminophenols using (o-CF3PhO)3P as a simple coupling reagent has been developed. Diverse benzothiazoles and benzoxazoles were synthesized in moderate to excellent yields. And the gram-scale preparation of benzothiazole and benzoxazole also proceeded smoothly under the mild conditions. Moreover, a plausible reaction mechanism was discussed, with (o-CF3PhO)3P and its hydrolysis product (o-CF3PhO)2P(O)H contributing to the formation of the target products as an amide synthesis coupling agent and a cyclization reaction promoter, respectively.

SMEs’ strategic orientation through Miles and Snow typology: a synthesis of literature and future directions

Purpose The purpose of this research is to present a systematic analysis of consequents and antecedents of strategy and performance. To acheive this, this systematic review article analyzes and synthesizes mainstream research on small and medium-sized enterprises (SMEs) where Miles and Snow typology was used for strategic orientation of the SMEs. The specific focus of the research is to develop a conceptual framework showing consequents and antecedents of the strategic orientation. Design/methodology/approach This study uses systematic literature review (SLR) method to identify, summarize and synthesize literature on Miles and Snow typology. Preferred reporting method for systematic reviews and meta-analyses to ensure adherence to systematic approach. The key words search consists of the words: “Miles and Snow”, “Miles and Snow” and “miles-snow” from Web of Science and Scopus databases for sample articles. Findings The trend of research on SMEs using Miles and Snow typology is on the rise with a shift from developed countries to the developing ones. Support for strategy-performance relationship hypotheses is overwhelming but the traditional view is in decline while new antecedent and consequent variables are being added. Mediator and moderating variables are also identified. Originality/value The SLR where a synthesis approach was applied for finding antecedents and consequent variables of strategy-performance relationship along with a presentation of conceptual framework makes this research unique. Additionally, the article presents the trends of research over the time based on timeframe, regions, methodological approaches and hypotheses support.

Electrocatalysts for Urea Synthesis from CO2 and Nitrogenous Species: From CO2 and N2/NOx Reduction to urea synthesis.

The traditional industrial synthesis of urea relies on the energy-intensive and polluting process, namely the Haber-Bosch method for ammonia production, followed by the Bosch-Meiser process for urea synthesis. In contrast, electrocatalytic C-N coupling from carbon dioxide (CO2) and nitrogenous species presents a promising alternative for direct urea synthesis under ambient conditions, bypassing the need for ammonia production. This review provides an overview of recent progress in the electrocatalytic coupling of CO2 and nitrogen sources for urea synthesis. It focuses on the role of intermediate species and active site structures in promoting urea synthesis, drawing from insights into reactants' adsorption behavior and interactions with catalysts tailored for CO2 reduction, nitrogen reduction, and nitrate reduction. Advanced electrocatalyst design strategies for urea synthesis from CO2 and nitrogenous species under ambient conditions are explored, providing insights for efficient catalyst design. Key challenges and prospective directions are presented in the conclusion. Mechanistic studies elucidating the C-N coupling reaction and future development directions are discussed. The review aims to inspire further research and development in electrocatalysts for electrochemical urea synthesis.

Regulation of Surface Oxygen Vacancies on Ce-Based Catalysts for Dimethyl Carbonate Direct Synthesis from CO2 and CH3OH

Regulation of Surface Oxygen Vacancies on Ce-Based Catalysts for Dimethyl Carbonate Direct Synthesis from CO₂ and CH₃OH

Synthesis of a gallic acid-based self-healing waterborne polyurethane with a thermo-responsive dynamic phenol-carbamate network for enhanced mechanical strength, antimicrobial activity, and shape memory properties

To expedite the advancement of multifunctional next-generation smart materials, it is imperative to create polymers derived from renewable, green bio-based resources. This paper presents a direct synthesis of thermo-responsive aqueous polyurethanes by combining gallic acid (GA) with isocyanate groups to form a dynamic phenol-carbamate crosslinked network and the incorporation of the metal-organic framework Cu-MOF-2 for synergistic effects. The resulting GA-based polyurethane (MOF-GWPU) exhibits excellent thermal stability and mechanical properties, achieving an ideal balance between mechanical strength and self-healing efficiency. The MOF-GWPU film demonstrates strong antimicrobial efficacy against Escherichia coli and Staphylococcus aureus, highlighting its exceptional antibacterial performance. The thermo-responsive dynamic covalent bonds enable the MOF-GWPU film to rapidly revert from a temporary shape back to its original form. Post-processing experiments further indicate that the crosslinked GA-PU polymer can be efficiently recycled through solution casting and hot-pressing techniques. This design offers a novel approach and valuable insights for advancing the development of multifunctional smart polymers derived from bio-based resources.

Enhancing the selective catalytic oxidation of lignocellulosic biomass to formic acid using hydrogen peroxide and a reusable MgAl hydrotalcite-derived as a catalyst in a green solvent

Biofuels or liquid fuels derived from natural matter, are one of the most intriguing yet divisive alternatives for petroleum-based fuels. The most common approach to produce biofuels is to transform plant sugars and other carbohydrates into oxygen-deficient chemicals. A growing relevance has been devoted in the direct synthesis of platform molecules from biomass resources, using one-pot or cascade techniques via adequate catalytic system tuning and improvement of the reaction conditions which have merged as a beneficial strategy from an economic and ecological standpoint. In a similar vein, the major objective of this contribution was to investigate and enhance the conditions for a selective oxidation of lignocellulosic biomass-derived cellulose to yield formic acid (FA), the latter is one of the most coveted liquid hydrogen carriers and among the key compounds used in the pharmaceutical, cosmetic, and leather industries. Both oxidizing aqueous hydrogen peroxide and calcined heterogeneous hydrotalcite catalyst have been employed at an atmospheric pressure for this purpose. The effect of reaction time, temperature, amount of catalyst and oxidant on the product's yield and selectivity have been investigated. The oxidation of a plant-derived cellulosic fiber at 70 °C using an H2O2 excess (7 mmol) provided an impressive result with a high yield and TON of 61.0 %, 12.30 respectively, the latter was confirmed to be relatively close to the one from the oxidation of pure cellulose. Furthermore, the reusability of the catalyst has also been studied which was demonstrated to result in the same yields for one reuse and 3 recycles.

Direct Synthesis of 3,4‐Disubstituted Quinolines and 2‐Acylquinolines from Amines and Epoxides

Herein, we present a protocol starting from styrene oxide reacting with o‐acylaniline and o‐alkenylaniline derivatives to obtain 3,4‐disubstituted quinoline and 2‐acylquinoline derivatives, respectively, in 32‐92% yields under specific conditions. Preliminary research outcomes underscore the versatility of our approach, as exemplified by its scalability for large‐scale synthesis, downstream derivatization, and the characteristic properties manifested by the modified molecules.

Molybdenum‐Catalyzed Direct Synthesis of Pyrroles from Nitroarenes with Glycols as Reductants

A molybdenum‐catalyzed synthesis of N‐(hetero)aryl pyrroles directly from inexpensive and commonly available (hetero)nitroarenes via reduction with pinacol and annulation with 1,4‐dicarbonyls or cyclobutane‐1,2‐diols has been described. The process does not require an inert atmosphere and tolerates the presence of air and water. This non‐noble catalytic system shows high chemoselectivity, allowing a diverse range of potentially reducible functional groups such as alkynes, alkenes, halogens, cyano, and carbonyls. Moreover, this strategy enables the reuse of a waste byproduct as reactant, facilitating the formation of challenging 1,4‐dicarbonyls from accessible cyclobutane‐1,2‐diols used as reducing agents.

Synergistic Rh(II)- and Zn(II)-Catalyzed [3 + 3] Annulation of Diazoenals and α-Hydroxy Ketones for the Direct Synthesis of 2H-Pyrans, A Gateway Toward γ-Pyrones.

A new synergistic Rh(II)/Zn(II)-catalyzed [3 + 3] annulation has been developed between diazoenals and α-hydroxy ketones enabling the direct synthesis of 4-formyl-2H-pyrans. The reaction involves the formation of protic oxonium ylides from highly electrophilic Rh-enalcarbenoids followed by Zn-templated regioselective intramolecular aldol condensation. Subsequent investigations demonstrated that 4-formyl-2H-pyrans are unique precursors of γ-pyrones. The γ-pyrones were obtained via Et3N-mediated oxidative deformylation. Further, the triflic-acid-promoted double Schmidt reaction of 4-formyl-2H-pyrans provides synthetically important carboxamide-substituted 4-cyano 2H-pyrans.

An Emerging Solid‐State Electrolyte Reactor to Drive the Future of Electrochemical Synthesis

AbstractElectrochemical reactors, powered by renewable electricity, have garnered widespread attention for chemical synthesis due to their low energy consumption and pollution‐free features. However, the inherent design flaw of traditional electrochemical reactors has persistently hindered the advancement of electrochemical synthesis, as they result in low product concentrations, low purity, and continuous production issues. As a novel electrochemical reactor, the porous solid‐state electrolyte (PSE) reactor is elaborately designed to overcome the limitation by enabling the direct and continuous synthesis of pure products, possessing a modular and scalable structure with high efficiency, safety, and long stability. In this work, first, the distinctive design of the PSE reactor, highlighting its structural features, core components, and variable configurations, is introduced. Furthermore, the configuration‐relevant applications in electrosynthesis, such as formic acid, acetic acid, and hydrogen peroxide (H2O2) production, are summarized. Integrated applications are also discussed, along with potential domains for improvements and optimization. Finally, the future developmental directions of the PSE devices are thoroughly explored. By addressing its unique design attributes, showcasing its capabilities, and envisioning prospective refinements and diverse applications, the aim is to boost the progression of this transformative technology toward widespread commercialization and industrial adoption, thereby revolutionizing sustainable electrochemical synthesis.

Copper-enalcarbenoids: Rapid access to 1,7-disubstituted indoles via [4+2] benzannulation between diazoenals and N-substituted pyrroles

A highly electrophilic copper enalcarbenoid has been disclosed here for the first time for its carbenoid reactivity. The synthetic utility of the transient Cu-enalcarbenoids has been demonstrated in the Cu-catalyzed direct synthesis of 1,7-disubstituted indoles from diazoenals and N-substituted pyrroles. In this reaction, Cu-enalcarbenoid served as a 4[C] biselectrophilic synthon whereas pyrrole served as a 2[C] bisnucleophilie leading to [4+2] benzannulation.

Intergrowth MFI Zeolite with Inverse Al Zoning and Predominant Sinusoidal Channels for Highly Selective Production of Styrene.

ZSM-5 zeolites with accessible micropore architecture and tunable acid-base sites are important shape-selective catalysts. However, the presence of exposed straight channels and the external acid-base sites of conventional ZSM-5 has a negative impact on shape selectivity. Herein, we report on the direct synthesis of an intergrowth ZSM-5 zeolite mimicking the mortise-tenon joints. It can be revealed by various methods that the mortise-tenon ZSM-5 shows an inverse Al gradient from the surface to the core of the zeolite. More importantly, the sinusoidal channels predominantly opened to their external surfaces are constructed. The shape-selective capability of the ZSM-5 zeolite has been fully exploited due to the intrinsic inert external surface and unique sinusoidal channel features, thereby resulting in high styrene selectivity (>90%) and good catalytic stability (>100 h) in the toluene side-chain alkylation reaction. In addition, in situ DRIFTS confirms that this intergrowth ZSM-5 contributes to the formation of more active intermediates of HCOO* and H3CO*, which is another reason responsible for the superior performance.

Cross‐Scale Interface Engineering for Fabricating Super‐Strong and Super‐Tough Aramid nanofiber film

AbstractPoly (p‐phenylene terephthalamide) (PPTA), known for its exceptional mechanical properties under the brand name Kevlar, finds extensive use in high‐performance applications despite the challenges it presents in processing and integration with other materials. Existing top–down methods for preparing PPTA composites result in significantly reduced strength (<200 MPa) and toughness (<10 MJ·m−3) due to insufficient interfacial interactions, limiting their application. Here, a cross‐scale interface engineering strategy is reported for fabricating super‐strong and super‐tough PPTA composite films. At the microscale, a synergistic crosslinking strategy of physical entanglement and hydrogen bonding to crosslink PPTA nanofibers is employed. At the macroscale, the network using a cyclic freeze–thaw and the stretch‐drying method is reinforced. The PPTA nanofiber composite film is super‐strong (854.6 MPa), super‐tough (106.2 MJ·m−3), and has a high‐temperature resistance (300 °C). Moreover, the bottom–up approach enables the direct synthesis of PPTA nanofibers, significantly reducing the preparation time from 7 days to 0.5 h. Furthermore, it is demonstrated that the composite film can be integrated into a robust and intelligent sensing‐display device that responds to external mechanical and heat injuries for firefighter's protection. This work provides an efficient strategy for fabricating high‐performance PPTA composites, paving the way for their practical use as durable protective materials.

Photochemically Driven Palladium- Phosphinoacridine Catalysis: A Carboxylative Approach for Arylcarbamate Synthesis.

In this study, we demonstrate that phosphinoacridines are efficient bidentate ligands for palladium-catalyzed carboxylative C-N coupling reactions under blue LED irradiation. This method facilitates the direct synthesis of arylcarbamates using a range of non-activated aryl halides, such as iodides and bromides, with various amines under atmospheric pressure of CO2. The optimized conditions exhibit high tolerance to sensitive functional groups, resulting in very good to excellent yields of the desired products. This approach expands the scope of palladium-catalyzed carboxylation reactions and offers an environmentally friendly route to arylcarbamates.

Agile manipulation of the time-frequency distribution of high-speed electromagnetic waves

Controlling the temporal evolution of an electromagnetic (EM) wave’s frequency components, the so-called time-frequency (TF) distribution, in a versatile and real-time fashion remains very challenging, especially at the high speeds (> GHz regime) required in contemporary communication, imaging, and sensing applications. We propose a general framework for manipulating the TF properties of high-speed EM waves. Specifically, the TF distribution is continuously mapped along the time domain through phase-only processing, enabling its user-defined manipulation via widely-available temporal modulation techniques. The time-mapping operations can then be inverted to reconstruct the TF-processed signal. Using off-the-shelf telecommunication components, we demonstrate arbitrary control of the TF distribution of EM waves over a full bandwidth approaching 100 GHz with nanosecond-scale programmability and MHz-level frequency resolution. We further demonstrate applications for mitigating rapidly changing frequency interference terms and the direct synthesis of fast waveforms with customized TF distributions. The reported method represents a significant advancement in TF processing of EM waves and it fulfills the stringent requirements for many modern and emerging applications.

Self‐promoted Controlled Ring‐opening Polymerization via Side Chain‐mediated Proton Transfer for the Synthesis of Tertiary Amine‐pendant Polypeptoids

Proton transfer is essential in virtually all biochemical processes, with enzymes facilitating this transfer by optimizing the proximity and orientation of reactants through site‐specific hydrogen bonds. Proton transfer is also crucial in the rate‐determining step for the ring‐opening polymerization of N‐carboxyanhydrides (NCAs), widely used to prepare various peptidomimetic materials. This study utilizes side chain‐assisted strategy to accelerate the rate of chain propagation by using NCAs with tertiary amine pendants. This moiety enables hydrogen bond formation between the incoming NCA and the polymer amino growing end. The tertiary amine side chain of the NCA forms a proton shuttle, via a less constrained transition state, to facilitate the proton transfer process. Moreover, the tertiary amine side chains enable the precipitation of NCA monomers through in situ protonation during the monomer synthesis. This greatly facilitates the synthesis of these unreported monomers, allowing the direct controlled synthesis of tertiary amine‐pendant polypeptoids. This side chain‐promoted polymerization has rarely been reported. Additionally, the tertiary amine side chains, as widely used functional groups, endow the polymers with unique properties including pH‐ and thermo‐responsiveness, tunable pKas, and siRNA transfection capability. The self‐promoted synthesis, facile monomer preparation, and attractive properties make tertiary amine‐pendant polypeptoids promising materials for various applications.