Organic Transformations Research Articles

Tailoring catalysis at the atomic level: trends and breakthroughs in single atom catalysts for organic transformation reactions.

The utilization of precise materials in heterogeneous catalysis will provide various new possibilities for developing superior catalysts to tackle worldwide energy and environmental issues. In recent years, single atom catalysts (SACs) with excellent atom utilization and isolated active sites have progressed dramatically as a thriving sector of catalysis research. Additionally, SACs bridge the gap between homogeneous and heterogeneous catalysts and overcome the limitations of both categories. Current research on SACs is highly oriented towards the organic synthesis of high-significance molecules with promising potential for large-scale applicability and industrialization. In this context, this review aims to comprehensively analyze the state-of-the-art research in the synthesis of SACs and analyze their structural, electronic, and geometric properties. Moreover, the unprecedented catalytic performance of the SACs towards various organic transformation reactions is succinctly summarized with recent reports. Further, a detailed summary of the current state of the research field of SACs in organic transformation is discussed. Finally, a critical analysis of the existing challenges in this emerging field of SACs and the possible countermeasures are provided. We believe that SACs have the potential to profoundly alter the chemical industry, pushing the boundaries of catalysis in new and undiscovered territory.

Mushroom-Mediated Redox Reactions.

The application of biocatalysts in organic synthesis has grown significantly in recent years, and both academia and industry are continuously searching for novel biocatalysts capable of performing challenging chemical reactions. Mushroom is a rich source of ligninolytic and secondary metabolite biosynthetic enzymes, and therefore was consider as promising biocatalysts for organic synthesis. This review focused on the broad utilization potential of the mushroom-based biocatalysts and highlights key advances in mushroom-mediated organic transformations. It mainly includes reduction of ketone and carboxylic acids, hydroxylation of aromatic and aliphatic compounds, epoxidation of olefin, oxidative cleavage of alkene, and other uncommon reactions catalyzed by the whole-cells or purified enzymes of mushroom-origin. Overall, a comprehensive overview of the applications of mushroom as biocatalyst in organic synthesis is provided, which puts this versatile microorganism in the spotlight of further research.

The Impact of Exogenous Organic Matter on the Properties of Humus Compounds of Soils Developing on a Reclaimed Fly Ash Landfill

Fly ash does not contain organic matter to initiate soil-forming processes and the proper development of plant cover. Therefore, in the reclamation of fly ash landfills, an integrated approach is required, including the introduction of exogenous organic matter into the top layer of ash. This study assessed changes in the content and quality of organic matter in soils developing on a reclaimed fly ash landfill. This study included reclaimed areas without the introduction of EOM (RV_1—the direct introduction of plants) and with the introduction of EOM (RV_2—surface humus and RV_3—sewage sludge). In samples taken 15 years after reclamation, the contents of total organic carbon (TOC) and total nitrogen (TN), the fractional composition of organic matter, the susceptibility of organic matter to oxidation, and soil carbon management indices (carbon pool index (CPI), C lability (L), lability index (LI), and carbon management index (CMI)) were determined. The study results showed that the use of EOM in the reclamation of the ash dump significantly increased the content and improved the quality parameters of organic matter and thus influenced the initiation of the process of organic matter accumulation. In RV_1 soil, the accumulation of carbon resources was only found in the topsoil. An increase in carbon resources in the 15–40 cm layer was only noted in the variants in which EOM was introduced (RV_2 and RV_3). Carbon management indices showed that organic matter transformations covered only the top layers of these soils and were closely related to the EOM inflow. The interdependence of the CPI and L was most beneficial in the soil reclaimed with sewage sludge. In the soil of this reclaiming variant, the CMI had a value above 100, which indicates the initiation of the soil-forming process. Significant differences between the assessed reclamation variants were confirmed by means of PCA based on organic matter quality indicators. The organic matter content and quality indicators were the most favorable in the soil of variant RV_3. The obtained results confirmed that the introduction of EOM into the top layer of fly ash has a beneficial effect on the accumulation and quality indicators of organic matter and thus on the development of the soil-forming process in Technosols developing on a reclaimed fly ash landfill.

The recent progress in the field of the applications of isoxazoles and their hydrogenated analogs: mini review

Recent review of the general application of isoxazoles and isoxazolines has been done based on current state of the art in this area. Isoxazole and its analogues have majority of possible applications in many fields of plural branches of industry. They possess good biological activity, so most of them are being used successfully in medicine and veterinary. These heterocyclic compounds could be also very important precursors of many organic transformation. Due to their easy modification, general interest of their development still increases.

Aminoborate-Catalyzed Reductive Counterreactions for Oxidative Electrosynthetic Transformations.

Electrooxidative transformations frequently rely on proton reduction as the terminal electron sink. However, this cathodic counterreaction can be slow in organic solvents and can operate at reducing potentials that are incompatible with catalysts and reagents needed for oxidative reactions. We report aminoborate adducts as redox mediators for proton reduction that operate at mild reducing potentials. This reliable cathodic couple ultimately enables successful oxidative organic transformations, including chlorodeborylation, developed herein, and Cu-catalyzed Chan-Lam coupling, reported previously by our group. Pyridinium borate adducts formed during electrooxidative chlorination of aryl trifluoroborates serve as easily reduced complexes (-1.1 V vs Fc/Fc+) to catalyze proton reduction. Reactions that promote the formation of borate adducts result in high yields, operate at low cell potentials, suppress aryl trifluoroborate decomposition, and mitigate electrode passivation. These studies illustrate the utility of Lewis acid-base complexes in cathodic counterreactions and underscore the importance of developing both anodic and cathodic reactions in electrosynthesis.

A Recent Update on the Visible Light-promoted Organic Transformations - A Mini-review.

Visible light-induced reactions are a rapidly developing and powerful technique to promote organic transformations. They provide green and sustainable chemistry and have recently received increasing attention from chemists due to their wide application in organic synthesis. Light energy is eco-friendly, cheap, green, and inexhaustible with potential industrial and pharmaceutical applications. In this review, the most recent advances in visible light-induced reactions (2021-till date) have been highlighted.

Surface self-modification of TiO2 for enhanced photocatalytic toluene oxidation via photothermal effect

Surface modification plays an important role in extending light absorption and enhancing the catalytic performance of semiconductor photocatalysts. However, most current studies focus on pre-modification of the semiconductors before reaction, while surface self-modification of catalyst during photocatalytic reaction process is often neglected. Here, we report the surface self-modification of TiO2 catalyst during photocatalytic oxidation of toluene under UV light irradiation, which changes the colour of TiO2 from white to yellow, and effectively extends its light absorption range into visible light region. The absorbed visible light is primarily released as thermal energy, significantly increasing the temperature of the catalytic system. Mechanistic studies reveal that the temperature elevation facilitates the separation of photogenerated charge carriers in TiO2 and promotes the generation of •O2−, consequently accelerating the surface redox reactions. The surface self-modified TiO2 exhibits an enhanced photothermal catalytic benzaldehyde generation of 4485 μmol g−1h−1 under UV–visible light irradiation, which surpasses the UV-driven activity of TiO2 by a factor of 1.9. This study offers new perspectives on the surface modification of semiconductor photocatalysts during organic transformations. It is anticipated to trigger increased research attention to this effect, ultimately advancing solar-to-chemical energy conversion.

Unusually high selectivity (100 %) of photocatalytic C[sbnd]C coupling achieved by instant reverse reduction of byproducts

The photocatalytic CC coupling of benzyl alcohol (BA) into hydrobenzoin (HB), is appealing to obtain high-value chemicals. However, the selectivity of HB is still low due to the inevitable formation of benzaldehyde. Herein, we report In(OH)3-ZnS photocatalyst for CC coupling of BA into HB with very high selectivity (∼100 %). The introduction of In(OH)3 onto ZnS with stable interaction facilitates light harvesting and separation of photo-excited charges. As a result, BA conversion on optimized In(0.1)-ZnS catalyst (73 %) is much higher than ZnS (29 %). Besides, the surface hydroxyl groups derived from In(OH)3 enables the facile desorption of CH(OH)Ph radical. Therefore, the over oxidation of CH(OH)Ph radical into by-product of benzaldehyde can be effectively inhibited. More significantly, in-situ FTIR spectra and reduction of by-product manifest the instant reverse reduction process of benzaldehyde into CH(OH)Ph radical during CC coupling of BA, which is the key to realizing satisfied HB selectivity (100 %). Theoretical simulations reveal that the weak adsorption of CH(OH)Ph radical over catalyst and the high energy barrier of over-oxidation of CH(OH)Ph into benzaldehyde contributes to the formation of highly selective coupling products. This work will inspire new insights to design rational photoredox systems for organic transformations with high selectivity

Solvent-Free Synthesis of Bioactive Heterocycles

: The main emphasis of green chemistry is to reduce environmental pollution. Its main goal is to adopt a cost-effective and harmless strategy for human health and the environment. The green synthetic routes have succeeded in adopting solvent-free conditions as an effective tool for sustainability. Heterocycles are organic compounds that are widely distributed by nature. Many of them possess medicinal and pharmacological properties, as this heterocyclic moiety is found in many drugs. The solvent-free strategies for the Synthesis of bioactive heterocycles are, now-adays, regarded as an important objective. Solvent-free reactions are eco-friendly, cost-effective, and an environmentally benign route in organic transformation methods because of their effi-ciency, reduced reaction time, and high yields, thereby saving energy. This mini-review focuses on the environmentally benign solvent-free Synthesis of heterocycles and their potential pharma-cological applications.

Interface Engineering: Enhanced Catalysis Through Precise Control of Metal Nanocluster Transformation.

Atomically precise metal nanoclusters (NCs) have garnered significant interest due to their unique atomic stacking structures, the effect of quantum confinement, and enriched active sites but suffer from thermal- or light-induced poor instability and self-aggregation, together with in situ self-conversion to conventional metal nanoparticles (NPs). How to effectively harness the generic detrimental self-transformation property of metal NCs has so far not garnered immense attention within the realm of catalysis. In this work, we develop a layer-by-layer assembly technology to accurately anchor metal NCs to the metal oxide matrix. Then, the anchoring of metal NCs to metal NPs is triggered by a simple thermal treatment that enables precise control over the interface structure, resulting in a hollow core-shell heterostructure with a metal core (Au, Ag) encapsulated by a metal oxide (CeO2, Fe2O3, SnO2) shell. Benefiting from the synergistic interplay between metal NPs and the metal oxide substrate, such self-assembled metal NPs@metal oxide heterostructures display excellent catalytic activities and stability in the reduction of aromatic nitro compounds. The detailed catalytic mechanism is elucidated. Our work offers fresh impetus for the judicious utilization of the inherent instability of metal NCs for catalytic selective organic transformation.

Flexible Triboelectric Nanogenerators Based on Cadmium Metal-Organic Framework/Eethyl Cellulose Composites as Energy Harvesters for Selective Photoinduced Bromination Reaction.

The fabrication of self-driven systems with flexibility and tunable output for organic photoinduction is highly desirable but challenging. In this study, a 3D cadmium metal-organic framework (Cd-MOF) is synthesized and used as a filler for ethyl cellulose (EC) to create mechanically durable and flexible Cd-MOF@EC composite films. Due to its well-established platform with periodically precise structure nature, the outputs of Cd-MOF-based TENG are much higher than those of ligand-based TENGs. Furthermore, composite films with different doping ratios of Cd-MOF are employed to assemble Cd-MOF@EC-based triboelectric nanogenerators (TENGs). The results reveal that a doping ratio of 10 wt.% Cd-MOF in Cd-MOF@EC provides the highest TENG output. Subsequently, a flexible 10 wt.% Cd-MOF@EC-based TENG (FCEC-TENG), working in the contact-separation model, is constructed to harvest mechanical energy from the human body, demonstrating excellent output performance and stability. The energy harvested from FCEC-TENG can directly illuminate 14 commercial white light-emitting diodes (LEDs), providing visible light for the photoinduction of the bromination reaction, and generating bromide with good yield and tolerance. This study presents an effective method for constructing flexible MOF-based TENG for self-powered photoinduced organic transformation systems.

Fully Conjugated Microporous Polymers as Metal-Free Heterogeneous Photocatalysts for Organic Transformations.

Photoactive conjugated microporous polymers (CMPs) have recently received huge attention in photocatalytic organic transformations owing to their adjustable structure and functionality. However, commonly reported CMPs are synthesized through metal catalyzed coupling reactions, which require complicated product separation and result in increased costs. In this study, two sp2 carbon-linked CMPs are constructed by organic base induced Knoevenagel reaction using 2,6-dimethylbenzo[1,2-d:4,5-d']bisoxazole and aromatic polyaldehydes as co-monomers. The new benzobisoxazole-based polymer materials feature fully π-conjugated skeleton with broad visible-light absorption, permanent porosity as well as outstanding stability. Importantly, they can effectively induce many organic reactions such as C-3 thiocyanation of indoles under visible-light illumination and show broad substrate applicability and superior recyclability.

Recent Developments in the Photochemical Reactions of N‐Heterocyclic Compounds

The adoption of clean and renewable light sources is becoming increasingly prevalent in organic synthesis due to their welfare, workability and economic benefits. In recent times, photo‐redox catalysis has emerged as a valuable tool in organic transformations owing to its environmentally friendly nature and utilization of abundant resources. Since harmful or polluting reagents are not needed for the organic photochemical reactions, these reactions provide insights into sustainable processes and green chemistry. N‐Heterocyclic compounds (NHC’s) constitute fundamental structural motifs in numerous organic compounds and are widely encountered in natural products and pharmaceuticals with diverse biological activities. Consequently, investigations into the synthesis and modification of these NHC’s such as indole, carbazole, benzimidazole, quinoline, isoquinoline and pyridine hold particular significance for chemists and pharmacologists. This review provides an overview of the impact of photocatalysis on synthesis of NHC’s and their modification from 2019 to 2024. These transformations are achieved through the utilization of both metal photocatalysts (e.g., Ir, Pd, Co, Gd etc.) and non‐metallic photocatalysts (e.g., Eosin‐Y, 4CzIPN, Mes‐Acr+ClO4‐ etc.), or even without the necessity of photocatalysts. It is anticipated that this review will serve as a valuable resource for researchers delving into the promising realm of photocatalyzed transformations.

Stoichiometry-Regulated Synthesis of Three Adenine-Based Coordination Polymers for Catalytic Excellence through the Synergistic Amalgamation of Coordinative Unsaturation and Lewis Basic Sites.

Nucleobase adenine is a promising candidate for synthesizing fascinating coordination polymers (CPs) due to the presence of five potential metal-ion binding centers. In recent years, CPs have emerged as promising Lewis acid-base centers containing heterogeneous catalysts for a wide range of organic transformations. However, the crucial role of stoichiometric regulations of the starting materials and their consequential impact on catalytic performance are rarely studied. Herein, we have synthesized three adenine (Ad)-based cadmium CPs with 5-nitro isophthalic acid (H2NIPA) by a mixed linker approach by tuning the substrate's stoichiometric proportion. The single-crystal X-ray diffraction analysis of the synthesized CPs, SSICG-11, [Cd(Ad)(NIPA)(H2O)]·H2O; SSICG-12, [Cd(Ad)2(NIPA)(H2O)]; and SSICG-13, [Cd4(Ad)(NIPA)3]·H2O·DMF, reveals that these three compounds exhibit distinct asymmetric units, each reflecting varying precursor proportions. Due to their high chemical stability and the presence of both Lewis acidic-basic sites, SSICG-11-13 were employed as heterogeneous catalysts for Hantzsch and Strecker reactions. However, SSICG-12 is more efficient due to its capacity to form an open metal sites (OMSs) and the presence of a higher number of adenine moieties. Overall, this study demonstrated the stoichiometrically controlled synthesis of adenine-based CPs and dissected their efficiency as a heterogeneous catalyst by correlating their structures and compositions.

Unravelling the mechanistic ‘Black Box’ of heterogeneous condensation reactions catalyzed by aminosilicas

Primary amino-functionalized silicas (H2N-SiO2) are well known acid-base cooperative catalysts for many organic transformations, including carbon–carbon (C–C) bond forming condensation reactions, and much attention has been devoted to the elucidation of their action mode. However, to our surprise, the mechanism of Henry reactions and Knoevenagel condensations catalyzed by H2N-SiO2 is still paradoxical, and the identity of the actual base species, transition states, reactivity, and product selectivity, remain as debatable topics of discussion. Herein we propose a brand-new reaction mechanism for H2N-SiO2-catalyzed Henry reactions that overcomes all prior inconsistencies. With the aid of Hammett analysis and density functional theory (DFT) calculations, we have effectively identified several critical transition states and are able to explain reactivity and product selectivity. This study revealed that H2N-SiO2 catalyzed Henry reactions of aldehydes and nitro compounds follow the imine mechanism to afford olefin adducts as only possible products. In addition, we utilized our findings to comprehend the mechanism of Knoevenagel condensation, a comparable reaction, dispelling a more than two-decade old misconception regarding the nature of the active base involved.

Recent Progress on Organic Electron Donors (OEDs) Enabled Radical Reactions

AbstractOver the past few decades, organic transformations facilitated by small organic molecules have witnessed considerable advancements. Small organic molecules have been widely applied to the construction of various skeletons. However, reduction as one of the fundamental reactions is generally initiated by metal‐containing reducing agents, although the initial progress of organic electron donors (OEDs) enabled reductive cleavage of some chemical bonds had been achieved in 1990s. Due to their structural diversity and tunability, OEDs can overcome the limitations of metal‐based reducing agents, such as low selectivity and poor functional group tolerance as well as the environmental problems caused by substantial inorganic waste after reactions. Building on a brief historical overview of OED research, this review focuses on the rencent advancements of the OEDs promoted radical reactions. It covers the reduction of C−X (X=C, O, N etc.) single bonds, radical cyclization, intermolecular radical addition to unsaturated bonds, radical coupling, functionalization of aromatics, and C−H bond activation. Additionally, the mechanistic insights of the typical reactions are highlighted for well understanding of the reaction mode involving OEDs.

A Covalent Triazine Framework for Photocatalytic Anti‐Markovnikov Hydrofunctionalizations

AbstractPorous materials‐based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)‐based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C−N and C−O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron‐donating and ‐withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late‐stage functionalization of bio‐active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.

A Covalent Triazine Framework for Photocatalytic Anti-Markovnikov Hydrofunctionalizations.

Porous materials-based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)-based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C-N and C-O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron-donating and -withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late-stage functionalization of bio-active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.

Tailoring of Novel Ru (III) and Cr (III) Salen Complexes as Catalysts for a Sustainable and Green Synthesis of Dihydro‐tetrazolo [1,5‐a] thiazolo [4,5‐d] pyrimidin‐6‐yl morpholine: Experimental and Theoretical Approaches

ABSTRACTTwo novel Cr (III) and Ru (III) salen complexes based on {3,4‐Bis‐[(5‐chloro‐2‐hydroxy‐benzylidene)‐amino]‐phenyl}‐phenyl‐methanone ligand (CSAB) were synthesized. The complexes were characterized using various spectral and analytical methods. The catalytic performance of the CSAB complexes was investigated via a four‐component condensation reaction involving aromatic aldehydes, rhodamine, morpholine, and 5‐aminotetrazole under mild, environmentally friendly conditions. Different Lewis acids, bases, ionic liquid catalysts, solvents, and catalyst amounts were assessed to optimize the reaction parameters. Both catalyst systems demonstrated robust catalytic activity under strictly managed conditions, with the heterogeneous catalyst CSAB‐Ru showing superior efficacy compared to the homogeneous CSAB‐Cr catalyst. The study confirmed the catalytic capabilities of both complexes and evaluated their recyclability and reusability. The heterogeneous catalyst (CSAB‐Ru) could be reused seven times, whereas the homogeneous catalyst (CSAB‐Cr) could be recycled four times. Both complexes demonstrated strong catalytic activity and selectivity, resulting in high product yields. The study provides insights into the synthetic applications of novel CSAB complexes, highlighting their potential in organic transformations. It emphasizes their ease of use, safety, stability, component availability, quick reaction times, and high yields, making them promising for future industrial applications.

Humic Substances from Waste-Based Fertilizers for Improved Soil Fertility

This research explores how different organic waste transformation methods influence the production of humic substances (HSs) and their impact on soil quality. Using olive and orange wastes as substrates, the study compares vermicomposting, composting, and anaerobic digestion processes to determine which method produces the most humic-substance-rich products. The characterization of HSs in each product included analyses of total organic carbon (TOC), humic and fulvic acid content, humification rate, humification degree, and E4/E6 ratio, with HSs extracted using potassium hydroxide (KOH) and analyzed via Diffuse Reflectance Infrared Fourier-Transform (DRIFT) spectroscopy to assess structural complexity. The results revealed that the chemical composition of the input materials significantly influenced the transformation dynamics, with orange by-products exhibiting a higher humification rate and degree. Vermicomposting emerged as the most efficient process, producing fertilizers with superior humic content, greater microbial biodiversity, and enhanced cation exchange capacity, thus markedly improving soil quality. Composting also contributed to the stabilization of organic matter, albeit less effectively than vermicomposting. Anaerobic digestion, by contrast, resulted in products with lower levels of HSs and reduced nutrient content. Aerobic processes, particularly vermicomposting, demonstrated the most rapid and effective transformation, producing structurally complex, stable humus-like substances with pronounced benefits for soil health. These findings underscore vermicomposting as the most sustainable and efficacious approach for generating HS-rich organic fertilizers, presenting a powerful alternative to synthetic fertilizers. Furthermore, this study highlights the potential of organic waste valorization to mitigate environmental pollution and foster circular economy practices in sustainable agriculture.