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This study presents a population balance model for the kinetics of nucleation and growth in covalent organic framework (COF) synthesis. The model incorporates second-order nucleation and first-order growth rates, consistent with proposals in the literature. Despite having non-linear terms, an implicit analytic solution is derived and then converted to explicit solutions for the monomer concentration and size distribution of COF flakes as a function of time. For experimental definitions of the induction time and the initial growth rate based on yield (y) vs time (t) curves, the model predicts power-law relationships: t ind = 0.409 k N − 1 / 3 k G − 2 / 3 c A 0 − 1 and d y / d t max = 0.965 k N 1 / 3 k G 2 / 3 c A 0 , respectively. We discuss the implications for the interpretation of Arrhenius plots. We also discuss key discrepancies with experiments, including the predicted attainment of 100% yield instead of 30%–40% as observed and the value of the yield at the inflection point in the yield vs time curve. We suggest extensions to the model, including nucleation and growth kinetics with equilibrium solubility limitations and two-dimensional nucleation for the formation of multilayer COF particles. [ABSTRACT FROM AUTHOR]

Transition-metal-catalyzed asymmetric allylic substitution reactions represent a hot research topic in the field of asymmetric synthesis, with significant progress having been made. Among diverse catalysis systems, relay catalysis enables sequential activation of multiple steps in one pot and the rapid construction of multiple chiral centers, providing a simple and powerful platform for organic synthesis. Recently, relay catalysis has been successfully applied to asymmetric allylic substitution reactions, and a variety of challenging transformations have been realized. This Short Review summarizes the related progress on asymmetric allylic substitution reactions based on relay catalysis over the last decade. 1 Introduction 2 The General Transformation Model 3 Allylation Relays Further Reaction 4 Initial Reaction Relays Allylation 5 Conclusion and Outlook [ABSTRACT FROM AUTHOR]

In this study, N, N-dibenzylaniline, an essential intermediate with broad significance in organic syntheses organic synthesis, was synthesized and characterized based on its spectrum. The single-crystal structure of the compound was confirmed using X-ray. The crystal structure of the compound, as calculated and optimized by DFT, was consistent with the crystal structure obtained by X-ray single-crystal diffraction. The functional groups of the compound were analyzed using vibrational analysis. Molecular docking analysis revealed the potential pharmacological effects of the compound. The molecular electrostatic potential and frontier molecular orbitals of the compound were studied, and its physical and chemical properties were revealed. [ABSTRACT FROM AUTHOR]

Herein, we disclose a highly efficient and facile electrochemical borylation of Morita–Baylis–Hillman adducts without using any metal catalyst. This methodology demonstrates excellent regio- and stereo-selectivity, leading to a wide range of functionalized E-allylic boronates, including derivatives of ibuprofen and menthol. Under mild and straightforward conditions, this redox-neutral reaction, combined with the scalability and synthetic applications of the allylic boronate esters, underscores its potential for a wide range of applications in organic synthesis. [ABSTRACT FROM AUTHOR]

The synthesis of nitrogen‐containing heterocyclic compounds using heterogeneous catalysis is a topic of significant interest in organic synthesis and chemical research. Heterogeneous catalysis offers several advantages over homogeneous catalysis, including easier separation and recovery of the catalyst, reduced waste generation, and potentially higher stability and reusability. In this review, the pivotal role of heterogeneous catalysis in synthesizing nitrogen‐containing heterocyclic compounds is explored. Various types of heterocycles and the specific applications of these compounds in drug discovery and material development are discussed in detail. This review discusses various examples of heterogeneous catalysts employed in the synthesis of nitrogen‐containing heterocycles, including metal oxides, supported metals, metal nanoparticles, zeolites, and other porous materials. Emphasis is placed on the mechanistic insights and reaction pathways facilitated by different catalysts. Additionally, recent advancements and innovations in the field are discussed, including novel catalyst designs, green chemistry approaches, and emerging trends in catalytic materials. The aim is to provide a comprehensive overview of the impact and potential of heterogeneous catalysis in this important area of organic synthesis. [ABSTRACT FROM AUTHOR]

Naturally occurring substituted benzoic acids, known for their exceptional biological activity against Pseudomonas aeruginosa, were reacted with various aldehydes, aniline, and tert‐butyl isocyanide at 25 °C to give the desired hybrids with good to excellent yield in the range of 60–85 % and well characterized by 1H NMR, 13C NMR, HRMS, IR, and HPLC analysis. Molecular docking and simulation studies of compounds were conducted which predicted a high affinity towards quorum‐sensing (QS) receptors of P. aeruginosa. The polyphenolic hybrids were first screened for anti‐QS activity using the Agrobacterium tumefaciens NTL4 biosensor strain, followed by examining the antivirulence potential of selected hybrids against P. aeruginosa PAO1 in vitro. The highest degree of AHL (acyl homoserine lactone) inhibition in PAO1 was observed with the compound having a maximum number of phenolic groups. The hybrids in this investigation were also found to be non‐cytotoxic (biocompatible) towards HEK cells and may be further tested for their therapeutic efficacy against P. aeruginosa infections in vivo. It has been observed that the anti‐QS activity is directly proportional to the number of hydroxyl groups on the aromatic ring and one of the major contributing factors can be their chelating capacity as depicted by CAS shuttle assay. [ABSTRACT FROM AUTHOR]

Industrial production of H2O2 requires lots of energy and causes environmental pollution. Moreover, in subsequent applications, much economic loss could be produced during the transportation process of H2O2 and its dilution process. Therefore, it is highly desirable for in situ application of H2O2. In recent years, catalytic synthesis of H2O2, e. g., direct catalytic synthesis, electrocatalytic synthesis, and photocatalytic synthesis, has attracted more and more attention because the continuous and low‐concentration H2O2 produced by catalytic synthesis can be directly used for the oxidation of organic compounds, effectively avoiding the shortcomings of the current industrial route. Here, we briefly reviewed the latest processes for the catalytic production of H2O2 via various routes. On this basis, we summarized and discussed the in situ application of H2O2 in typical organic conversion reactions, including the ammoximation of ketones, the oxidation of alcohols, the oxidation of C−H bonds, and the oxidation of olefins. Some in situ coupling reactions have shown excellent performance with high conversion and selectivity, and the economic cost has been significantly reduced. Finally, the shortcomings of the in situ utilization of H2O2 in coupling reactions were analyzed, and some strategies for promoting the efficiency of the H2O2 application in organic synthesis were proposed. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs), at the forefront of porous materials, hold tremendous potential in membrane separation; however, achieving high continuity in COF membranes remains crucial for efficient gas separation. Here, we present a unique approach termed assembly‐dissociation‐reconstruction for fabricating COF membranes tailored for CO2/N2 separation. A parent COF is designed from two‐node aldehyde and three‐node amine monomers and dissociated to high‐aspect‐ratio nanosheets. Subsequently, COF nanosheets are orderly reconstructed into a crack‐free membrane by surface reaction under water evaporation. The membrane exhibits high crystallinity, open pores and a strong affinity for CO2 adsorption over N2, resulting in CO2 permeance exceeding 1060 GPU and CO2/N2 selectivity surpassing 30.6. The efficacy of this strategy offers valuable guidance for the precise fabrication of gas‐separation membranes. [ABSTRACT FROM AUTHOR]

In this Short Review, we discuss radical reactions using 1,2-bis(phenylsulfonyl)ethylene (BPSE), which has drawn significant attention as a versatile building block for (phenylsulfonyl)ethenylation. Regardless of its E or Z form, BPSE exhibits reliable reactivity towards the attack of alkyl and aryl radicals in order to function as a reliable radical C2 synthon. 1 Introduction 2 Use in Radical Chain Reactions 3 Use in Reactions Utilizing an Electron-Transfer Process 4 Use in Radical-Based C–H Alkenylation 5 Conclusion [ABSTRACT FROM AUTHOR]

Research on synthetic methods for the preparation of oxazoles is an important issue among synthetic chemists because oxazole derivatives are structural subunits of various natural active products and are valuable synthetic and pharmaceutical precursors. In this research work, we constructed CuBr supported on surface of magnetic Fe3O4 nanoparticles modified with 6-(aminomethyl)nicotinic acid [Fe3O4@AMNA-CuBr nanocomposite] and evaluated its catalytic activity for the preparation of highly substituted oxazoles through one-pot three-component reactions of diphenylacetylene derivatives with aryl nitriles and water in PEG as the solvent. The results shown that the Fe3O4@AMNA-CuBr catalyst was used 8 times without significant decrease in catalytic activity. XRD and TEM analysis confirmed that the structure and morphology that the Fe3O4@AMNA-CuBr catalyst did not change after 8 runs. [ABSTRACT FROM AUTHOR]

In this study, we report a simple, green, effective, and enhanced method for synthesizing pyranopyrazole from four-component condensation of aldehyde, malononitrile, ethyl aceto-acetate, and hydrazine hydrate employing four components in one pot that is multicomponent reactions (MCRs). Multicomponent reactions carried out by using a universal solvent; water has a quality position in organic and green synthesis. By using an aqueous hydrotropic solution and ultra-probe sonication, raising the rate of reaction and getting an excellent yield are the main features of this article. Key features of the current practice include the use of non-hazardous reaction conditions, operational simplicity, and the use of cost-effective initiating substances. The pure product can be isolated easily through simple filtration, eliminating the need for column chromatography. The process yields excellent results and is time-efficient. Additionally, the hydrotrope can be recycled up to five times without significant loss of activity, making it highly beneficial for meeting industrial needs and addressing environmental concerns. [ABSTRACT FROM AUTHOR]

This document is a profile of Jinfa Chang, a new editorial board member of Frontier Reporters for the Chinese Journal of Chemistry. Chang is a professor at Northeast Normal University in China and has a background in chemistry, with a focus on electrocatalytic hydrogen energy-electric energy conversion. Chang's research aims to design and develop cost-effective, high-performance catalysts to accelerate the commercialization of hydrogen-related energy storage and conversion technologies. The lab pays particular attention to the electrocatalytic performance of electrode materials for fuel cells and water electrolysis under real-service conditions, with a specific interest in the reaction mechanism and structure-performance relationship. [Extracted from the article]

Comprehensive Summary: Concise assembly of spirooxindoles is of great significance but a challenging task in modern organic synthesis. Described herein is an unusual base‐promoted [4+2] spiroannulation of rarely used isatin‐derived β‐silylcarbinols with o‐halogen aromatic ketones, which enables rapid and modular synthesis of six‐membered carbocyclic spirooxindoles in high yields with excellent functional group tolerance (> 50 examples). Mechanistic experiments revealed that this reaction involved a Peterson olefination, Michael addition and intramolecular C(sp3) arylation cascade. The variegated synthetic derivatization of target products and successful construction of bioactive molecules further illustrate the synthetic potential in spirooxindole‐related drug discovery. [ABSTRACT FROM AUTHOR]

The conductance of a tunneling electron through a π-conjugated molecule may be affected by the presence of different pathways in the orbital structure of the molecule, resulting in the constructive or destructive interference of the molecular wave function. This quantum interference (QI) directly translates into enhancement or suppression of conductance and offers the possibility of controlling this phenomenon through tailored synthesis. Hence, we set up synthetic methodologies to access a series of thiophene-fused helicenes with a well-defined positioning of the sulfur atoms, which control the occurrence of conducting, linearly conjugated as well as disrupted, cross-conjugated pathways. We describe these synthetic strategies and relate the expected electronic transport through our molecules to three key variables: a) the exo-/endo-topology of the S atom within the ring; b) the parity (odd/even) of the overall number of rings conforming to the helicene; and c) the size of the circuit. This series ranks from [7] to [11] fused rings, having both exo-, endo-, or mixed exo-endo-topology. Comparison of homologous dithiahelicenes with size-tunable highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energies allows us to isolate the key variable of the bond topology from other electronic properties and face the study of QI in helically conjugated molecules. Understanding and tuning the conductance in such molecular solenoids is the main purpose of this work. [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]

In the past 20 years, unspecific peroxygenases (UPOs) have emerged as promising biocatalysts for various organic transformations. Particularly, we have witnessed great attention being paid to the screening of new enzymes and expansion of the substrates/products. However, challenges such as enzyme stability, low turnover numbers, and substrate specificity hinder their widespread utilization in practical organic synthesis. This review article provides a concrete and mini-overview of the challenges associated with using UPOs in organic synthesis and discusses strategies for enzyme engineering to overcome these limitations. The article highlights recent advancements in UPO research and presents potential solutions to enhance their catalytic efficiency, stability, substrate specificity, and regioselectivity. Additionally, the review outlines the current methodologies employed for directed evolution and protein engineering of UPOs, along with computational modeling approaches for rational enzyme design. By addressing the challenges and exploring avenues for enzyme engineering, this review aims to shed light on the prospects of UPOs in organic synthesis. [ABSTRACT FROM AUTHOR]

Axially chiral allenes bearing organoboron groups are highly sought-after building blocks in organic synthesis due to their potential for generating a wide range of axially and centrally chiral molecules. However, the existing methods for preparing axially chiral allenes containing boron group are primarily limited to the synthesis of allenyl boronic esters, and strategies for accessing axially chiral homoallenyl boronic esters are still scarce. Here, we report the general method for synthesizing axially chiral α-boryl-homoallenyl boronic esters through a highly regio- and stereoselective copper-mediated SN2'-addition of newly prepared (diborylalkyl)copper species to chiral propargyl electrophiles. The reaction conditions were optimized to achieve high yields and excellent stereospecificity. The obtained products were successfully transformed into various axially chiral allenes and other chiral molecules by transforming diboron units. The potential for axial-to-central chirality transfer of axially chiral α-boryl-homoallenyl boronic esters is also demonstrated through the stereospecific addition to aldehydes and N-H aldimines, yielding enantioenriched 1,2-oxaborinin-3,5-dienes and 2-aminomethyl-1,3-dienes. Axially chiral allenes are important building blocks in organic chemistry due to their potential for functionalization, which can be enhanced by the presence of a synthetically flexible organoboron group. Here, the authors report a stereospecific synthesis of axially chiral alpha-boryl-homoallenyl boronic esters from enantioenriched propargyl carbonates, mediated by copper. [ABSTRACT FROM AUTHOR]

A simple and sustainable propylphosphonic anhydride (T3P)-assisted methodology for the synthesis of N-acyl tryptamines, an interesting class of gut microbiota-derived endocannabinoid-like lipid mediators, was proposed. This protocol is characterized by great operational simplicity, and all products were obtained at room temperature, without the use of an inert atmosphere and by using limited amounts of non-halogenated solvents. Finally, the possibility to realize the reaction under mechanochemical conditions was explored with interesting results. [ABSTRACT FROM AUTHOR]

Metal‐free synthesis of heterocycles is highly sought after in the pharmaceutical industry and has garnered widespread attention due to eliminating the need to remove trace metal catalysts from the reaction. We report a radical 6‐endo addition method for pyridine synthesis from cyclopropylamides and alkynes under metal‐free conditions. Various terminal and substituted alkynes are inserted as C2 units into cyclopropylamides to synthesize versatile pyridines with 57 examples. Mechanistic investigations and computational studies indicate the unprecedented 6‐endo‐trig addition of vinyl radicals to the imine nitrogen atom rather than the conventional 5‐exo‐trig addition to the imine carbon atom, in which the hypervalent iodine(III) plays a critical role. This reaction easily scales up with excellent functional group compatibility and suits the late‐stage pyridine installation on complex molecules. [ABSTRACT FROM AUTHOR]

Allylic amines are prevalent and vital structural components present in many bioactive compounds and natural products. Additionally, they serve as valuable intermediates and building blocks, with wide‐ranging applications in organic synthesis. However, direct α‐C(sp3)−H alkenylation of feedstock amines, particularly for the preparation of α‐alkenylated cyclic amines, has posed a longstanding challenge. Herein, we present a general, mild, operationally simple, and transition‐metal‐free α‐alkenylation of various readily available amines with alkenylborate esters in excellent E/Z ‐ and diastereoselectivities. This method features good compatibility with water and oxygen, broad substrate scope, and excellent functional group tolerance, thereby enabling the late‐stage modification of various complex molecules. Mechanistic studies suggest that the formation of a photoactive electron donor‐acceptor complex between 2‐iodobenzamide and the tetraalkoxyborate anion, which subsequently undergoes photoinduced single electron transfer and intramolecular 1,5‐hydrogen atom transfer to generate the crucial α‐amino radicals, is the key to success of this chemistry. [ABSTRACT FROM AUTHOR]

This Minireview examines a selection of case studies that showcase distinctive and enabling electrochemical approaches that have allowed for the generation and reaction of carbocation intermediates under mild conditions. Particular emphasis is placed on the progress that has been made in this area of organic synthesis and polymer chemistry over the past decade. [ABSTRACT FROM AUTHOR]

Since the milestone contribution by Chen and White in 2007, bioinspired non‐heme bis‐amino‐bis‐pyridylmethyl Fe complexes have been at the forefront of studies related to designing catalytic approaches for direct oxidative functionalization of aliphatic C−H bonds. This, however, has not developed into large‐scale synthetic applications to date. The present concept is aimed at briefly discussing the state‐of‐the‐art of non‐heme Fe catalyzed oxidations of organic molecules with H2O2, the current oxidant of choice of bioinspired oxidation catalysis, mostly focusing on C−H oxidations, and analyzing the peculiarities of their reactivity through the prism of potential applications in fine organic synthesis. [ABSTRACT FROM AUTHOR]

The aqueous alteration of the oceanic lithosphere provides significant energy that impacts the synthesis and diversity of organic compounds, which are crucial for the deep carbon cycle and may have provided the first building blocks for life. Although abiotic organic synthesis has been documented in mantle-derived rocks, the formation mechanisms and complexity of organic compounds in crustal rocks remain largely unknown. Here, we show the specific association of aliphatic carbonaceous matter with Fe oxyhydroxides in mafic crustal rocks of the Southwest Indian Ridge (SWIR). We determine potential Fe-based pathways for abiotic organic synthesis from CO2 and H2 using multimodal and molecular nano-geochemical tools. Quantum mechanical modeling is further employed to constrain the catalytical activity of Fe oxyhydroxides, revealing that the catalytic cycle of hydrogen may play a key role in carbon–carbon bond formation. This approach offers the possibility of interpreting physicochemical organic formation and condensation mechanisms at an atomic scale. The findings expand our knowledge of the existence of abiotic organic carbon in the oceanic crustal rocks and emphasize the mafic oceanic crust of the SWIR as a potential site for low-temperature abiotic organic synthesis. [ABSTRACT FROM AUTHOR]

The synthesis of sulfoxides has long attracted considerable interest due to their pivotal role in organic synthesis, pharmaceutics and environmental protection. Oxidation of the corresponding sulfides is recognized as the most effective strategy. Traditional oxidation methods, however, fall short of the growing demands of green chemistry. Photocatalytic aerobic oxidation has thus garnered attention, employing the greenest and most sustainable oxidants—oxygen or air—and sunlight as the energy source. Nevertheless, these reactions are typically conducted in potentially pollutive organic solvents rather than in the greenest solvent, water. To facilitate this organic transformation in aqueous phase, molecular reactors that can encapsulate reactants within their confined pores and facilitate photocatalytic reactions have been developed recently. This Concept article summarizes the development of molecular reactors for the photocatalytic oxidation of sulfides and provides perspectives for the design and construction of effective photocatalytic molecular reactors. [ABSTRACT FROM AUTHOR]

The establishment of all‐carbon quaternary carbon centers represents a pivotal aspect in the synthesis of numerous natural products and pharmaceutical compounds, underscoring its paramount significance in synthetic organic chemistry. Herein, we present a novel synthetic strategy for the generation of quaternary carbon centers through the reductive coupling of tertiary halides, catalyzed by dinuclear (salen)titanium catalysts. This catalytic framework demonstrates notable reactivity towards tertiary chlorides while maintaining inertness towards secondary and primary chlorides, thereby facilitating exceptional chemoselectivity for C−C bond formation. The reaction proceeds with remarkable efficiency across a diverse range of substrates under mild reaction conditions. [ABSTRACT FROM AUTHOR]

Dehydrogenative coupling (DC) and borrowing hydrogen(ation) (BH) reactions are crucial in modern organic synthesis, offering efficient and sustainable ways to create valuable compounds. However, they often face a significant challenge: the alkoxide trap. This Concept explores the alkoxide trap in DC and BH reactions, starting with the basic mechanisms and the role of alkoxide intermediates. It then examines how the alkoxide trap leads to catalyst deactivation and reduced selectivity, influenced by thermodynamic and kinetic factors. To address this, we review recent advances in catalyst design, ligand engineering, and optimized reaction conditions, along with the use of in‐situ spectroscopy and computational modelling, to better understand the underlying processes and guide rational catalyst development. Furthermore, this Concept highlights the broad applicability of DC, and BH reactions across various substrates, underscoring the urgency of addressing the alkoxide trap issue to unlock their full synthetic potential. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) are emerging as promising heterogeneous photocatalysts for organic transformations, owing to their fascinating optical properties, excellent recyclability, and customizable chemical structures. To maximize the photocatalytic activity of COFs, various strategies have been explored, including metal complexation, construction of donor‐acceptor structures, modification of functional groups, hybridization with inorganic semiconductors, and linkage conversion. Among these, linkage conversion has proved to be particularly effective, driving the production of numerous value‐added organic chemicals. In this concept article, we present a comprehensive overview of the latest advancements in linkage conversion and highlight the most enlightening examples that have adopted such a strategy to boost the photocatalytic capabilities of COFs for organic transformations. It is anticipated that this concept will assist researchers in designing novel COFs with multifunctional linkages, paving the way towards their broader application in organic synthesis. [ABSTRACT FROM AUTHOR]

Pyrrole‐embedded organic molecules received a considerable importance due to their numerous biological and material applications. Hence, several synthetic strategies have been devised for the construction of diverse pyrrole analogues over the years. Among these, the Clauson‐Kaas reaction is one of the most widely used protocols for the synthesis of various N‐substituted pyrroles. This review briefly describes the Clauson‐Kaas reaction along with modifications and a detailed account on its applications in the various sectors of organic synthesis. [ABSTRACT FROM AUTHOR]

The selective borylation of specific C−H bonds in organic synthesis remains a formidable challenge. In this study, we present a novel spirobipyridine ligand that features a binaphthyl backbone. This ligand facilitates the iridium‐catalyzed selective C−H borylation of benzene derivatives. The ligand is designed with "side‐arm‐wall" substituents that allow vicinal di‐ or multi‐substituted benzene derivatives to approach metal center and effectively block other reactive sites by non‐covalent interactions with substrates. The effectiveness of this strategy is demonstrated by the successful selective distal C−H activation of various alkaloids and its broad compatibility with functional groups. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (g‐C3N4) assisted photocatalytic production of hydrogen peroxide (H2O2 has already attracted the interest of many researchers due to its environmental sustainability. Nevertheless, the inherent drawbacks of g‐C3N4 limit its progress. Metal‐free modification strategies, including nanostructure design, defect introduction, doping, and heterojunction construction, have been developed to improve the efficiency of g‐C3N4 photocatalytic H2O2 production. Compared to metal modification, metal‐free strategies avoid the use of precious metals and the leaching of heavy metal ions, which have the advantages of good stability and environmental friendliness. However, a comprehensive review of H2O2 production from g‐C3N4 modified by metal‐free strategies is still lacking. This review first recaps the mechanism of photocatalytic H2O2 production by g‐C3N4, including photoexcitation, carrier separation and redox reactions. Then, the perspective advances in metal‐free modified g‐C3N4 photocatalysts are presented, with the special focus on the kernel connection between different strategies and mechanism based on the pivotal stages of H2O2 production. Subsequently, recent applications of g‐C3N4‐based photocatalysts for in situ generated H2O2, mainly including water purification and organic synthesis, are briefly discussed. Finally, the prospects of g‐C3N4‐based photocatalysts are envisioned with the hope that it will have "something to do" in the field of H2O2 production. [ABSTRACT FROM AUTHOR]

AbstractPhotocatalytic materials have garnered a lot of interest in recent decades for their effective use in solar energy harvesting. Fullerenes have drawn interest in a number of applications, particularly in the field of photocatalysis, owing to its remarkable qualities, which include great stability in chemical form, an extensive specific surface area, superior electrical conductivity, and a peculiar zero-dimensional carbon nanoallotrope. The use of fullerenes as zero-dimensional carbon nanomaterials for photocatalytic applications has been well studied. Fullerene-based photocatalysts have been applied and developed in areas such as organic synthesis, aerobic oxidation, photodyanamic therapy, CO2 reduction, H2 creation, and degradation of pollutants. This review attempts to give a broad summary of the most recent findings in fullerene-based photocatalyst research. [ABSTRACT FROM AUTHOR]

Silicon, due to its abundance, non‐toxicity, and cost‐effectiveness, is a critical element in the earth's crust with significant industrial applications. In organic chemistry, main group elements, and in particular silicon, are extensively utilized as versatile synthetic intermediates. Despite the current challenges associated with harsh reaction conditions and unsustainable practices in synthesizing crucial organic structural molecules, desilylation reactions have emerged as a facilitative method, offering milder conditions and operational simplicity. This review provides a comprehensive analysis of recent advancements in the synthesis of valuable organic molecules through two distinct desilylation reactions. It systematically presents the synthesis of a variety of derivatives, such as furan, alcohol, N‐heterocyclic, and ketone, highlighting the broad substrate tolerance of these reactions. This broad functional group compatibility suggests a promising future for the synthesis of a wide range of bioactive molecules, underscoring the significant potential of desilylation in contemporary organic synthesis. [ABSTRACT FROM AUTHOR]

The current throughput of conventional organic chemical synthesis is usually a few experiments for each operator per day. We develop a robotic system for ultra-high-throughput chemical synthesis, online characterization, and large-scale condition screening of photocatalytic reactions, based on the liquid-core waveguide, microfluidic liquid-handling, and artificial intelligence techniques. The system is capable of performing automated reactant mixture preparation, changing, introduction, ultra-fast photocatalytic reactions in seconds, online spectroscopic detection of the reaction product, and screening of different reaction conditions. We apply the system in large-scale screening of 12,000 reaction conditions of a photocatalytic [2 + 2] cycloaddition reaction including multiple continuous and discrete variables, reaching an ultra-high throughput up to 10,000 reaction conditions per day. Based on the data, AI-assisted cross-substrate/photocatalyst prediction is conducted. The current throughput of conventional organic chemical synthesis is usually a few experiments for each operator per day. Here the authors develop a robotic system for ultra-high-throughput chemical synthesis, online characterization and large-scale condition screening of photocatalytic reactions. [ABSTRACT FROM AUTHOR]

A simple and efficient strategy has been developed for the synthesis of organic nitrate esters via visible‐light‐induced multi‐component nitrooxylation reactions of α‐diazoesters, cyclic ethers, and tert‐butyl nitrite under open air atmosphere. This transformation could be conducted under mild and metal‐free conditions to provide a number of organic nitrate esters in moderate to good yields using air as the green oxidant. [ABSTRACT FROM AUTHOR]

Developing novel and environmentally friendly green methodologies are critical in synthetic organic chemistry. Here, we investigated the one‐pot, efficient green synthesis of pyrazolo[3,4‐b]pyridine derivatives via a multicomponent approach. The reactions were operated in an aqueous medium by using microwave irradiation and conventional protocols. The green protocol offered high yields of desired product in swift reaction time, and good tolerance under reaction conditions. [ABSTRACT FROM AUTHOR]

Site‐selective amination of N‐heterocycles is an interesting topic in organic synthesis and drug discovery. We herein present a method for the vicarious‐type nucleophilic amination of azine N‐oxides and cyclic iminoamides using iminyl anions, readily generated from organic azides under basic conditions. The plausible reaction mechanism involving nucleophilic aromatic substitution by iminyl anions is elucidated by a series of mechanistic investigations. [ABSTRACT FROM AUTHOR]

Our study introduces a streamlined oxidative method for synthesizing 1,3‐diarylphenanthro[9,10‐c]thiophenes, and their subsequent oxidative cleavage to yield 9,10‐diaroylphenanthrenes. Harnessing an optimized aerobic photochemical transformation, we showcase broad substrate scope and tolerance to various photosensitive functional groups. Our mechanistic investigations unveil the pivotal role of singlet oxygen, providing intriguing insights into the reaction pathway. The synthesized 9,10‐diaroylphenanthrenes serve as versatile building blocks for nitrogen‐containing heterocycles, dibenzoannulated phthalazines, that are promising compounds with diverse functionalities. Offering mild conditions, and broad applicability, our synthetic strategy is useful for organic synthesis and chemical biology exploration. [ABSTRACT FROM AUTHOR]

Hypervalent iodine reagents are versatile and readily accessible reagents that have been extensively applied in contemporary synthesis in modern organic chemistry. Among them, iodonitrene (ArI=NR), is a powerful reactive species, widely used for a single‐nitrogen‐atom insertion reaction, and skeletal editing to construct N‐heterocycles. Skeletal editing with reactive iodonitrene components has recently emerged as an exciting approach in modern chemical transformation. These reagents have been extensively used to produce biologically relevant heterocycles and functionalized molecular architectures. Recently, the insertion of a nitrogen‐atom into hydrocarbons to generate N‐heterocyclic compounds using hypervalent iodine reagents has been a significant focus in the field of molecular editing reactions. In this review, we discuss the rapidly emerging field of nitrene insertion, including skeletal editing and nitrogen insertion, using hypervalent iodine reagents to access nitrogen‐containing heterocycles, and the current mechanistic understanding of these processes. [ABSTRACT FROM AUTHOR]

The origin of life (OoL) has always been a mysterious and challenging topic that puzzles human beings. Clay minerals have unique properties and wide distribution in early Earth environments. They can not only adsorb biological small molecules to catalyze their polymerization, but play an active role in the formation and evolution of protocells. In this review, the research progress on the interactions of clay minerals with biomolecules and protocells complex structures in the field of the OoL based on chemical evolution theory is summarized. The types, structures and properties of clay minerals, biological molecules and protocell models related to the OoL are introduced in detail. The mechanism of interaction between clay minerals and biological molecules, the construction of protocells and the role of clay minerals in the formation, structure and stability of protocells are systematically described. Finally, the future research priorities and challenges in the field of OoL based on clay minerals, biomolecules and protocells are discussed. It is aspired that this review can further advance the exploration of the OoL from a new perspective, and can also bring some interesting findings and ideas to the interdisciplinary research of materials, biology, chemistry and other related disciplines.Clay minerals have a variety of interactions with small biomolecules, which can be used as structural and functional templates to promote the organic synthesis of biomolecules and the formation and evolution of protocells, playing a non‐negligible role in the field of the OoL. [ABSTRACT FROM AUTHOR]

Functionalized arenes, such as aniline and phenol derivatives, are important structures in natural products, drug molecules, and functional materials. Thus, the development of methods for the efficient synthesis of functionalized arenes from different precursors under mild conditions have been a long‐term topic in organic synthesis and related areas. To date, great efforts have been devoted the Ar−X bond‐forming processes from aromatic precursors. In addition, synthesis of functionalized arenes from aliphatic architectures represents an attractive yet challenging alternative to access functionalized arenes, which construct aromatization during the reaction process along with the formation of C−X bonds. Recently, a new strategy for functionalized arenes from non‐aromatic precursors enabled by radicals has received considerable attention and represents a new direction to access functionalized arenes from broader precursors at room temperature. [ABSTRACT FROM AUTHOR]

Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC systems suffer from limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO4 photoanodes with tailored deposition layers for customizing two PEC approaches toward C−N and C−P bond formation. Our process proceeds under mild reaction conditions, deploying easily available substrates and ultra‐low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications. [ABSTRACT FROM AUTHOR]

The selective and controllable functionalization of unreactive C(sp3)–H bonds under mild conditions is a highly desirable yet challenging goal in both organic synthesis and pharmaceutical industry. Herein, we report an unprecedented visible-light mediated metal- and oxidant-free carbonylation of both benzylic and allylic C–H bonds with H2O. The synergistic combination of an organophotocatalyst 4CzIPN and a thiol enables the transformation of diverse arrays of benzylic and allylic C–H bonds into carbonyls in moderate to excellent yields with good functional group compatibility. Moreover, the oxidation of amines to aldehydes has also been realized by this protocol. Mechanistically, an oxidative radical-polar crossover (ORPC) process affords an alcohol intermediate, which then undergoes another ORPC process to furnish the carbonyl product. [ABSTRACT FROM AUTHOR]

Differentiating between two highly similar C–H bonds in a given molecule remains a fundamental challenge in synthetic organic chemistry. Directing group assisted strategies for the functionalisation of proximal C–H bonds has been known for the last few decades. However, distal C–H bond functionalisation is strenuous and requires distinctly specialised techniques. In this review, we summarise the advancement in Pd-catalysed distal C(sp2)–H and C(sp3)–H bond activation through various redox manifolds including Pd(0)/Pd(II), Pd(II)/Pd(IV) and Pd(II)/Pd(0). Distal C–H functionalisation, where a Pd-catalyst is directly involved in the C–H activation step, either through assistance of an external directing group or directed by an inherent functionality or functional group incorporated at the site of the Pd–C bond is covered. The purpose of this review is to portray the current state of art in Pd-catalysed distal C(sp2)–H and C(sp3)–H functionalisation reactions, their mechanism and application in the late-stage functionalisation of medicinal compounds along with highlighting its limitations, thus leaving the field open for further synthetic adjustment. [ABSTRACT FROM AUTHOR]

The efficiency of photocatalysts depends largely on the accessibility of reaction species to the active centre, the electron transfer and geometric matching between the active surface of the catalyst and reaction species. In this work, we successfully synthesized and designed one two-dimensional Mn(II) MOF with [Mn2(H2L1)(H2O)2(DMF)2]n·(CH3CH2OH)n (HSTC 3) by using MnCl2·4H2O and 5,5′-(anthracene-9,10-diyl)diisophthalic acid (H4L1), in which the adjacent layers are stacked with weak interactions, and the huge gap leads to the interpenetration between layers to form a 2D + 2D → 3D interpenetration frame. Based on the particularity of the structure of HSTC 3, ultrasonic wall breaking methods were tried to successfully peel HSTC 3 into nanosheets (HSTC 3-NS), thus achieving a significant improvement in a series of optoelectronic properties due to exposure to more active centres for HSTC 3-NS. These results significantly enhance the photocatalytic selective oxidation of thioether. This study provides a new insight into the post-synthesis modification of MOF photocatalyst and their application in photocatalytic organic synthesis. [ABSTRACT FROM AUTHOR]

There is an increasing demand for the development of catalytic reagents that are nontoxic due to the growing environmental concerns in the present organic transformation. Bismuth(III) compounds have significant potential as catalysts for a range of organic synthesis due to their low toxicity, strong Lewis acid catalytic activity, and great flexibility. In this research work, a series of various chemically and pharmacologically important six‐membered fused nitrogen‐/oxygen‐based heterocycle derivatives were efficiently prepared via a one‐pot multicomponent reaction starting from aromatic aldehydes, malononitrile, and barbituric acid in presence of green and reusable Lewis catalyst bismuth(III) triflate, that is, Bi(OTf)3 in EtOH/H2O (1:1) media. Bi(OTf)3 has the additional benefit of being reusable catalyst, ready availability, eco‐friendliness, and easy to handle to obtain corresponding products in excellent yields (83%–94%). Structure of all synthesized products was characterized on the basis of FT‐IR, 1H‐NMR, 13C‐NMR, and ESI–MS analysis. [ABSTRACT FROM AUTHOR]

Sulfonamides have been played a critical role in the history of medicinal chemistry development for decades. In particular, sulfonamides display a broad spectrum in pharmaceutical drugs synthesis. This review presents a short discussion of the microwave‐assisted synthetic approaches, enhancement of sulfonamides moieties and their pharmacological applications are being discussed. During the past few decades, microwave‐assisted technology in organic synthesis has been highlighted to introducing ‐SO2NH functional group in the multi synthetic routes for the development of bioactive molecule and also assisted in the estimation of their credible mechanistic routes for the reactions. [ABSTRACT FROM AUTHOR]

The indole moiety, a prevalent and versatile heterocyclic scaffold, plays a pivotal role in the realm of organic synthesis, underpinning the structural basis of myriad natural products, pharmaceuticals and advanced materials. This review comprehensively surveys the landscape of methodologies for indole synthesis, highlighting the evolution of techniques from classical to contemporary strategies. We investigate the Fischer Indole Synthesis, emphasizing its historical significance and mechanistic nuances and transition to discussing the Reissert Indole Synthesis, detailing its unique contributions to the synthesis of indole derivatives. Furthermore, the review explores advanced methodologies including metal-catalyzed reactions, C-H activation processes and green synthesis approaches, offering insights into their mechanisms, scope and limitations. Through this review, we aim to provide a holistic overview of indole synthesis, furnishing researchers with a detailed understanding of its complex mechanisms and the broad utility of the indole moiety in synthesizing biologically active compounds. The synthesis methods reviewed not only underscore the chemical diversity and adaptability of indole chemistry but also highlight ongoing challenges and future directions in the synthesis and transformation of derivatives of indole. This comprehensive examination serves as a valuable resource for chemists seeking to harness the indole scaffold's potential in novel synthetic applications. [ABSTRACT FROM AUTHOR]

Geraniol is a compound belonging to the group of monoterpenes that finds many applications in organic syntheses, medicine and cosmetics. The following properties of geraniol and its derivatives are of particular interest in medicine: its anti-inflammatory, antioxidant, antimicrobial and anticancer effects. The geraniol oxidation process was carried out using a mineral of natural origin—vermiculite. Vermiculite is a catalyst that perfectly fits into modern trends in the organic industry, where the aim is to use cheap, renewable and relatively easily available catalytic materials (vermiculite is found on continents including Africa, North America, South America, Australia and Asia). Preliminary studies on the oxidation process of geraniol on vermiculite was carried out in a glass apparatus using molecular oxygen supplied by means of a bubbler and magnetic stirrer with a heating function. During the oxidation process of geraniol on vermiculite, the influence of the following parameters was examined: the temperature, amount of catalyst and reaction time. The main parameters of the process, on the basis of which the most favorable process conditions were selected, were the selectivity of the transformation to 2,3-epoxygeraniol, citral and 2,3-epoxycitral, and the conversion of geraniol. The composition of the post-reaction mixtures was determined qualitatively and quantitatively using the gas chromatography method. In addition, vermiculite was subjected to instrumental tests, such as XRD, SEM, EDX, FTIR and UV-VIS. Moreover, the specific surface area, pore volume and pore volume distribution were estimated on the basis of N2 sorption at −196 °C and also the acid-site concentration in vermiculite was established. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs), newly developed materials, exhibit considerable promise in the field of catalysis. COFs exhibit captivating catalytic characteristics, including thermal and chemical stability, customizable porosities, and the ability to place active sites flexibly with tunable functions. To establish a connection between structure and activity, this paper provides a thorough justification of the planned creation of covalent organic frameworks for photocatalysis, encompassing H2 production, carbon dioxide reduction, pollutants reduction and transformation of organic substances. We have investigated the catalytic sites that are active within covalent organic frameworks, encompassing the metals, molecular catalysts, and catalyst with single atom (SACs); the reactive skeleton/linkages; and the reactive pendant groups. This exploration aims to establish the benefits of using COF‐based catalysts compared to traditional catalysts. Despite the new advantages, numerous difficulties have also been noted with regard to the future. The objective of this review is to make it easier to design COF‐based composite materials for practical uses. [ABSTRACT FROM AUTHOR]

This review introduces the synthetic organic chemical value of α‐bromocarbonyl compounds with tertiary carbons. This α‐bromocarbonyl compound with a tertiary carbon has been used primarily only as a radical initiator in atom transfer radical polymerization (ATRP) reactions. However, with the recent development of photo‐radical reactions (around 2010), research on the use of α‐bromocarbonyl compounds as tertiary alkyl radical precursors became popular (around 2012). As more examples were reported, α‐bromocarbonyl compounds were studied not only as radicals but also for their applications in organometallic and ionic reactions. That is, α‐bromocarbonyl compounds act as nucleophiles as well as electrophiles. The carbonyl group of α‐bromocarbonyl compounds is also attractive because it allows the skeleton to be converted after the reaction, and it is being applied to total synthesis. In our survey until 2022, α‐bromocarbonyl compounds can be used to perform a full range of reactions necessary for organic synthesis, including multi‐component reactions, cross‐coupling, substitution, cyclization, rearrangement, stereospecific reactions, asymmetric reactions. α‐Bromocarbonyl compounds have created a new trend in tertiary alkylation, which until then had limited reaction patterns in organic synthesis. This review focuses on how α‐bromocarbonyl compounds can be used in synthetic organic chemistry. [ABSTRACT FROM AUTHOR]