Radical Pathway Research Articles

Radical‐Driven Imine Hydrogenation Promoted by the Cooperativity of Nickel and a Redox‐Active Ligand

AbstractIn the case of N‐alkylation reaction via borrowing hydrogen (BH) methods, imine hydrogenation is one of the critical steps. Mechanistically, the majority of imine hydrogenation, either by dihydrogen gas or by alcohol in case of BH methods, follow two‐electron chemistry, where a metal‐hydride intermediate plays a pivotal role. Herein we demonstrate a completely complementary protocol, where the hydrogenation is governed by a radical pathway. Such a pathway is adopted from the redox active nature of the azophenolate ligand backbone. The facile and reversible 2e−/2H+, azo/hydrazo redox couple in a nickel catalyst helps in storing the hydrogen from alcohol dehydrogenation. An imine substrate is reduced by one‐electron from the azo motif with the assistance of the nickel center. The reduced imine drives a critical hydrogen atom transfer step from the hydrazo motif to conduct the hydrogenation. A set of kinetics experiments including Eyring analysis, radical inhibition experiment along with computational probation attest for the radical‐promoted hydrogenation mechanism.

C(sp3)−F Bond Activation by Lewis Base‐Boryl Radicals via Concerted Electron‐Fluoride Transfer

AbstractSelective C−F bond activation through a radical pathway in the presence of multiple C−H bonds remains a formidable challenge, owing to the extraordinarily strong bond strength of the C−F bond. By the aid of density functional theory calculations, we disclose an innovative concerted electron‐fluoride transfer mechanism, harnessing the unique reactivity of Lewis base‐boryl radicals to selectively activate the resilient C−F bonds in fluoroalkanes. This enables the direct abstraction of a fluorine atom and subsequent generation of an alkyl radical, thus expanding the boundaries of halogen atom transfer reactions.

General Alkene 1,2-syn-Cyano-Hydroxylation Procedure Via Electrochemical Activation of Isoxazoline Cycloadducts.

Stereoselective alkene 1,2-difunctionalization is a privileged strategy to access three-dimensional C(sp3)-rich chiral molecules from readily available "flat" carbon feedstocks. State-of-the-art approaches exploit chiral transition metal-catalysts to enable high levels of regio- and stereocontrol. However, this is often achieved at the expense of a limited alkene scope and reduced generality. 1,3-Dipolar cycloadditions are routinely used to form heterocycles from alkenes with high levels of regioselectivity and stereospecificity. Nevertheless, methods for the ring-opening of cycloadducts to reveal synthetically useful functionalities require the use of hazardous reagents or forcing reaction conditions; thus limiting their synthetic applications. Herein, we describe the implementation of a practical, general and selective electrosynthetic strategy for olefin 1,2-syn-difunctionalization, which hinges on the design of novel reagents-consisting of a nitrile oxide 1,3-dipole precursor, equipped with a sulfonyl-handle. These can selectively difunctionalize alkenes via "click" 1,3-dipolar cycloadditions, and then facilitate the telescoped electrochemical single electron transfer activation of the ensuing isoxazoline intermediate. Cathodic reduction of the cycloadduct triggers a radical fragmentation pathway delivering sought-after stereodefined 1,2-syn-hydroxy nitrile derivatives. Our telescoped electrochemical procedure tolerates a wide range of functionalities, and─crucially─enables the difunctionalization of both electron-rich, electron-poor and unactivated olefins, with diverse degree of substitution; thus providing a robust, general and selective metal-free alternative to current alkene difunctionalization strategies. Capitalizing on these features, we employed our electrosynthetic method to enable the late-stage syn-hydroxy-cyanation of natural products and bioactive compounds, and streamline the de novo synthesis of pharmaceutical agents.

Cu-Catalyzed Hydrodechlorination of Unactivated Alkyl Chlorides Using Diisobutylaluminum Hydride.

A copper-catalyzed hydrodechlorination of primary, secondary, and tertiary alkyl chlorides using diisobutylaluminum hydride is reported. This catalytic system offers a broad substrate scope, high yields, and good functional group tolerance. Mechanistic investigations indicated that the reaction predominantly proceeds via a radical pathway, as supported by radical clock experiments. Importantly, this study provides a new approach for the selective hydrodechlorination of unactivated alkyl chlorides and expands the utility of Cu-hydride catalysis in sustainable chemical synthesis.

Highly Efficient Activation of Peroxymonosulphate by Co and Cu Co-Doped Sawdust Biochar for Ultra-Fast Removal of Bisphenol A

The rapid, efficient, and thorough degradation of Bisphenol A (BPA) is challenging. In this study, we prepared an effective peroxymonosulphate (PMS) activation catalyst derived from sawdust containing calcium carbonate. The Co and Cu co-doped sawdust biochar (CoO/CuO@CBC) catalyst could activate PMS quickly, and the degradation rate of BPA reached 99.3% in 5 min, while the rate constant was approximately 30 times higher than in the CBC/PMS and CoCuOx/PMS systems. Moreover, the interaction between CoO, CuO, and CBC endows the CoO/CuO@CBC catalyst with excellent catalytic performance under different conditions, such as initial pH, temperature, water matrix, inorganic anions, and humic acid, which maintained fast PMS activation via the cyclic transformation of Cu and Co for BPA degradation. The results demonstrated that both the radical (•O2− and •SO4−) and non-radical (1O2) pathways participate in the degradation of BPA in the CoO/CuO@CBC/PMS system. The efficient and stable degradation over a wide range of pH, temperature, and aqueous matrices indicates the potential application of the CoO/CuO@CBC catalyst.

Cu(I)-Catalyzed Silylation and Germylation of Azauracils.

The current study demonstrates a Cu(I) catalyzed direct C(sp2)-H silylation and germylation of azauracil using triphenylsilane and triphenylgermane. A broad scope, excellent functional group tolerance, and suitability for large-scale reactions are exhibited in this protocol. Moreover, this method can be readily applied to structurally complex bioactive molecules. Experimental results suggest a radical mechanistic pathway for the reaction.

N-heterocyclic carbene switchable radical or benzyne meditated arylation of thiols using DMF/KOtBu

A mild, metal and photoredox-free direct arylation of alkyl and aryl thiols with aryl iodides using a DMF/KOtBu system has been developed. In the absence of an N-heterocyclic carbene (NHC) additive, the reaction proceeds via a benzyne intermediate and was suitable for the substitution of thiols with phenyl, while the presence of an NHC or phenanthroline derivative improves regioselectivity for the reaction of substituted aryl iodides via a radical pathway. This protocol features inexpensive materials and good substrate scope, and could be useful in the arylation of aryl and alkyl thiols.

Catalyst Activation of Peroxymonosulfate for Reactive Species Generation and Organic Pollutant Degradation: A Mini Review

This review focuses on the application and mechanisms of peroxymonosulfate (PMS) in advanced oxidation processes (AOPs). It clarifies the significance of PMS in degrading organic pollutants, highlighting its high efficiency in treating persistent contaminants, such as antibiotics. The review details the roles and mechanisms of various catalysts, including single-atom catalysts, metal oxides, non-metal oxides and their composites, as well as metal-organic frameworks (MOFs), in activating PMS. It emphasizes the influence of catalyst surface active sites on both radical and nonradical activation pathways. Key factors affecting PMS activation efficiency, such as PMS concentration, pH value, coexisting ions, and temperature, are examined to underline the importance of optimizing these parameters for effective reaction conditions. By synthesizing existing research, the review not only illustrates the extensive application potential of PMS in AOPs but also identifies future research challenges and directions. This provides a theoretical foundation and technical support for developing efficient, economical, and sustainable water treatment technologies.

Fe3C@Fe decorated carbonized wood Fiber catalyst for organic dyes degradation: Preparation, characterization and mechanism

The extensive use of organic dyes has led to significant water pollution. Using lignocellulosic waste as a precursor for catalysts preparation for sewage remediation presents an effective alternative with numerous advantages in sustainability, cost-effectiveness, and environmental compatibility. In this work, wood fiber waste collected from wood processing plants was decorated with Prussian blue (PB) and then annealed to produce carbonized wood fiber catalyst (Fe3C@Fe-CB). In the presence of peroxymonosulfate (PMS), the prepared catalyst could achieve over 98.69 % efficiency in degrading methylene blue (MB) solutions (20 mg/L) in 60 min across a pH range of 3 to 11. Electrochemical test and electron paramagnetic resonance (EPR) analysis respectively verified that electron transfer pathway and radical pathway were the key factors for the degradation of MB. Cyclic degradation tests demonstrated that the degradation efficiency remained above 93.67 % after five recycling experiments. Moreover, the used magnetic catalyst can be easily recycled by magnet. This study proposed a facile and sustainable carbonized wood fiber catalyst decorated by Fe3C@Fe-CB, which could realize efficient elimination of organic dyes. Moreover, we offered a novel choice for dyes-polluted water treatment and paving a new route for converting low-value lignocellulosic waste to high-value utilizations.

Five novel Pb/Zn/Co metal-organic frameworks using 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene and carboxylate ligands: Synthesis, characterization, DFT calculation and catalytic PMS degradation of RhB

Five new metal-organic frameworks (MOFs), namely {Pb(atpt)(3-bpd)0.5}n (1); {Co(cbz)2(3-bpd)(H2O)2·2H2O}n (2); {Co(imdc)(3-bpd)(H2O)·H2O}n (3); {Co(tdca)(3-bpd)(H2O)2·DMF}n (4); {Zn(tdca)(3-bpd)(H2O)2·DMF}n (5), were assembled with metal ions Pb²⁺, Zn²⁺, and Co²⁺ using 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpd) as the main ligand, combined with 2-aminoterephthalic acid (H2atpt), 4-cyanobenzoic acid (Hcbz), 4,5-imidazoledicarboxylic acid (H2imdc), and thiophene-2,5-dicarboxylic acid (H2tdca) as auxiliary ligands via hydro/solvothermal methods. Their molecular structures were analyzed by single-crystal X-ray diffraction and characterized by FT-IR and PXRD. Complex 1 has a three-dimensional structure with a hepta-coordinated, semi-directed {PbNO6} metal center. The central metal ions in complexes 2–5 exhibit a six-coordinated {MN2O4} (M = Co or Zn) octahedral geometry. In complex 2, the carboxylate ligand does not function as a bridging ligand, resulting in a 1D chain structure, while complexes 3- 5 extend into 2D layered structures. Thermogravimetric analysis indicates good thermal stability for complexes 1–5. Then, the prepared complexes were used as catalysts to degrade Rhodamine B (RhB) during the monopersulfate (PMS) activation. Complexes 3 and 4 demonstrated significant efficiency, achieving degradation rates of 93.61 % and 98.56 % within 10 min. Radical scavenging experiments and EPR analysis identified that the activation of PMS for dye degradation by the two catalysts occurs through both radical and non-radical pathways, with SO4•− and •OH radicals being the dominant species. Density functional theory (DFT) calculations explained the superior catalytic performance of complex 4 compared to complex 3.

Highly dispersed single-atom Fe and Fe3O4 clusters anchored hierarchical-pore carbon as efficient persulfate activation catalyst

The selective removal of Fe particles from carbonized Fe-MOFs presents an intriguing strategy for developing efficient peroxydisulfate (PDS) activators. It is commonly accepted that their outstanding performance is largely attributed to the high specific surface area/pore volume. However, our investigation into the structure–function relationship of these materials has revealed new insights. In this study, a highly dispersed single-atom Fe and Fe3O4 clusters anchored hierarchical-pore carbon (CM88-H) was obtained via post-acid treatment of carbonized MIL-88B (CM88). Various characterizations were comparatively conducted to highlight the beneficial effects of iron dissolution. The CM88-H/PDS system achieved a notable BPA degradation efficiency, with a reaction rate of 0.323 min−1, which is 3.94 times higher than that of the CM88/PDS system. DFT calculations indicate that the Fe3O4 clusters optimize the charge distribution around single-atom Fe, promoting favorable PDS adsorption and facilitating a higher oxidation state of CM88-H. As a result, BPA can be completely degraded within 10 min with 0.1 g/L CM88-H and 0.05 g/L PDS via both radical and non-radical pathways. The CM88-H/PDS/BPA system performs effectively under various conditions, with a general reduction in toxicity. Furthermore, the CM88-H/PDS system shows broad oxidation activity towards BPA substitutes and pollutants with high ionization potential (IP). Notably, the CM88-H sponge-based fixed-bed catalytic reactor demonstrated satisfactory BPA degradation, highlighting the promising application of CM88-H in water purification. This study provides a sustainable solution for water treatment and accelerates the practical application of powdered nanocatalysts to improve water quality.

Influence mechanism of divalent metals in the laminates of M2+Al-layered double hydroxides on peroxymonosulfate activation reaction pathway: Radical vs nonradical

Radical and nonradical reaction pathways have been commonly validated in peroxymonosulfate (PMS) based advanced oxidation progresses (AOPs) using layered double hydroxides (LDHs) as catalysts, but achieving efficient and selective degradation of organic pollutants remains challenging due to the unclear regulatory mechanism of laminate M2+ in PMS activation. Here, the d-orbital electrons configuration of M2+ was found to influence the degree of overlap between M−OH and O of PMS, which results in the selective dissociation of PMS to form reactive oxygen species (ROS) or achieve electron transfer pathway. Further analysis revealed that Co(II, 3d7) and Ni(II, 3d8) with filled 3d orbital electrons can serve as electron donors for PMS, leading to the cleavage of O–O bond and the efficient generation of radical-based ROS. In contrast, Mg(II, 3d0) with unfilled 3d orbital electrons and Zn(II, 3d10) with full filled 3d orbital electrons tend to act as electron shuttles, and the outermost orbitals substantially overlap with the O of PMS to form metastable complexes. Consequently, MgAl-LDH interacts with PMS to selectively degrade quinolones as electron donor through electron transfer pathway, and its performance was not inhibited by common anions and organic matter in actual water. The above results provide a basis for optimizing the design of LDH-based catalysts according to the type of laminate M2+ to achieve high selectivity and efficiency of PMS-AOPs in water purification applications.

Mechanistic insights into the roles of copper in enhanced peroxymonosulfate activation for tetracycline degradation by copper ferrite composite catalyst

Tetracycline (TC) pollution has attracted great attention due to its wide use, non-biodegradability and potential carcinogenicity. Bimetallic catalysts/peroxymonosulfate (PMS) systems have been considered as powerful technologies for TC degradation. Although the excellent catalytic activity of copper ferrite (CuFe2O4) composite oxides for PMS has been already elucidated, the roles of increased Cu in the degradation especially from non-radical pathways are not clarified clearly. In this study, we prepared a series of CuO/CuFe2O4/Fe2O3 (CCF) catalysts to confirm the key role of molar ratios of Cu: Fe (ranging from 1:2 to 2:1) in the enhanced degradation. The optimized CCF-3 catalyst with the Cu: Fe molar ratio of 2:1 showed the best degradation efficiency up to 95.6 % and the fastest apparent degradation rate of 0.135 min−1 towards TC. In addition, the CCF-3/PMS system showed excellent adaptability and good stability in TC degradation. Importantly, a novel molecular-scale mechanism was proposed. Both radical (SO4∙-, ∙OH, O2∙ –) and non-radical (1O2, direct electron transfer) pathways were associated with the CCF-3/PMS catalytic system, where 1O2 played the dominant roles. The increased Cu significantly boosted the non-radical pathways via promoting the formation of oxygen vacancies (Ov) and its further conversion to 1O2, and facilitating electron transfer between bimetallic Cu/Fe interface. This work provides a deep insight into the formation and reaction mechanisms of non-radical species for CCF/PMS systems, and a novel foundation for the design of CuFe2O4 composite catalysts

Magnetic MgFeO@BC Derived from Rice Husk as Peroxymonosulfate Activator for Sulfamethoxazole Degradation: Performance and Reaction Mechanism.

Heterogeneous Mg-Fe oxide/biochar (MgFeO@BC) nanocomposites were synthesized by a co-precipitation method and used as biochar-based catalysts to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. The optimal conditions for SMX degradation were examined as follows: pH 7.0, MgFeO@BC of 0.4 g/L, PMS concentration of 0.6 mM and SMX concentration of 10.0 mg/L at 25 ℃. In the MgFeO@BC/PMS system, the removal efficiency of SMX was 99.0% in water within 40 min under optimal conditions. In the MgFeO@BC/PMS system, the removal efficiencies of tetracycline (TC), cephalexin (CEX), ciprofloxacin (CIP), 4-chloro-3-methyl phenol (CMP) and SMX within 40 min are 95.3%, 98.4%, 98.2%, 97.5% and 99.0%, respectively. The radical quenching experiments and electron spin resonance (ESR) analysis suggested that both non-radical pathway and radical pathway advanced SMX degradation. SMX was oxidized by sulfate radicals (SO4•-), hydroxyl radicals (•OH) and singlet oxygen (1O2), and SO4•- acted as the main active species. MgFeO@BC exhibits a higher current density, and therefore, a higher electron migration rate and redox capacity. Due to the large number of available binding sites on the surface of MgFeO@BC and the low amount of ion leaching during the catalytic reaction, the system has good anti-interference ability and stability. Finally, the intermediates of SMX were detected.

Linear Paired Electrolysis Enables Redox-Neutral (3 + 2) Annulation of Benzofuran with Vinyldiazo Compounds.

Electrosynthesis has emerged as a versatile and sustainable tool in organic chemistry, offering an efficient pathway for the construction of complex molecular architectures under mild and environmentally benign conditions. Traditional electrochemical approaches, however, predominantly rely on either anodic oxidation or cathodic reduction, limiting their capacity to achieve redox-neutral transformations using a single electrode. In this work, we introduce a linear paired electrolysis strategy that circumvents these limitations, enabling a redox-neutral (3 + 2) annulation of benzofuran with vinyldiazo compounds. This method facilitates the formation of benzofuran-fused tricyclic scaffolds, which are valuable in synthetic chemistry and medicinal applications. The transformation proceeds through sequential anodic oxidation and cathodic reduction, leveraging a radical cation pathway to deliver polycyclic compounds with high selectivity. The efficiency and mechanism of this process are thoroughly validated using cyclic voltammetry and in situ electrochemical mass spectrometry (EC-MS) and supported by theoretical calculations, shedding light on the potential of redox-neutral electrochemical transformations.

Activation of peroxymonosulfate by MnOOH/g-C3N5: Study on highly selective removal of phenolic pollutants and its non-radical pathway

In this research, the MnOOH/g-C3N5 material was successfully synthesized, demonstrating its efficacy in selectively removing phenolic organic pollutants. This material outperformed traditional free radical pathways, exhibiting higher selectivity, enhanced persulfate utilization efficiency, and strong resistance to background anions and complex organic matter. Using phenol as the target pollutant, the MnOOH/g-C3N5/PMS system achieved 81 % mineralization, a PMS utilization efficiency of 88 %, and a 75 % process unit energy consumption value in degrading phenol. This efficient degradation is attributed to the synergistic effects of high-valence metal oxides (MnV(O)/MnIV(O)), singlet oxygen (1O2), and electron transfer complexes, as confirmed by electrochemical analysis and In-situ EPR. Additionally, Transmission Electron Microscopy observations disclosed the development of an amorphous shell on the MnOOH/g-C3N5 surface post-reaction. Electrochemical Impedance Spectroscopy analysis suggested an enhanced charge transfer resistance, further affirming the role of MnOOH/g-C3N5 as an "electron transfer station" in the electron transfer process, accompanied by the formation of electron transfer complexes. This study provides crucial scientific insights and theoretical guidance for applying MnOOH/g-C3N5 materials in environmental engineering.

Solvent‐Free Dehydrogenative C−H Chalcogenations of Pyrazolones Using Mechanochemistry

AbstractA mechanochemical cross‐dehydrogenative coupling reaction of pyrazolones with thiols using ball milling is described. Benzeneselenol and dichalcogenide substrates are also compatible under mild reaction conditions, yielding up to 99 %. Notable features of this reaction include its metal‐ and solvent‐free, wide substrate scope and good functional group tolerance. Preliminary mechanistic investigations suggest that a radical pathway is likely involved in this C−H chalcogenation reaction.

Lewis Acid Catalyzed Cycloaddition Reaction of Bicyclo[1.1.0]butanes

In recent years, the formal cycloaddition reactions involving bicyclo[1.1.0]butanes (BCBs) have furnished an array of innovative methodologies and strategies for the efficient synthesis of bicyclo [2.1.1] hexanes (BCHs). Most methods can be broadly classified into two main modes: the radical pathway and the two-electron pathway. This Synpacts article will summarize the recent advancements in Lewis acid-catalyzed formal cycloaddition reactions involving BCBs with alkenes, dipolar molecules, and alkynes, spanning the period from 2022 to 2024. Additionally, we introduce the formal cycloaddition reaction of BCBs with ynamides, catalyzed by Sc(OTf)3, which has been recently developed by our group. This approach offers a novel and efficient method for the synthesis of polysubstituted 2-amino-bicyclo[2.1.1]hexenes.

A rapid and scalable method for visible light induced bromination of uracil derivatives in a falling film looping photoreactor.

Visible light induced green synthesis of 5-bromouracil derivatives using N-bromosuccinimide (NBS) in acetonitrile under batch operation with a constant photon flux of 46 μmol s-1 is reported. This methodology has shown excellent tolerance with various 6-substituted and N-substituted uracils and is also applicable for various pyrimidine and arene derivatives. The reaction proceeded through the formation of a bromine molecule via a radical pathway followed by an electrophilic substitution reaction, and this hybrid nature of the reaction pathway in the presence of light made the process faster. We successfully synthesized twenty-one derivatives and characterized them using various spectroscopic methods. Finally, the three different modules of the looping falling film reactor were used to show the successive scalability of the process with comparable photonic characteristics and reaction conditions. We achieved milligram to multigram scale reaction with almost equal efficiency and maximum productivity up to 1.2 kg per day.

Ornidazole degradation based on peroxymonosulfate activation induced by oxygen vacancies (OV)-enriched Cu-Co-TiO2: Coexistence of free-radical and non-radical pathways

Employing transition-metal catalysts in peroxymonosulfate (PMS) activation reactions to facilitate combined free-radical and non-radical interactions is regarded as a proficient approach for decomposing organic contaminants. However, the creation of active catalysts faces significant challenges due to low activation efficiency, inadequate action sites, and instability of current activation materials. Here, we successfully prepared bimetallic Cu and Co co-doped TiO2 (Cu-Co-TiO2) catalyst using the sol-gel technique. Excellent ornidazole (ONZ) removal efficiency (0.628 min−1) was demonstrated by the Cu-Co-TiO2/PMS system, which was applicable across a broad pH range (4−10) and unaffected by different water matrices. Moreover, the coexistence of free-radical (SO4•-, •OH and O2•−) and non-radical (1O2) routes in the Cu-Co-TiO2/PMS system, where SO4•- and 1O2 are the predominant active substances, was confirmed by quenching experiments and electron paramagnetic resonance (EPR) study. The synergistic impact of Cu/Co bimetal may hasten the redox cycles of Cu+/Cu2+ and Co2+/Co3+, causing plenty of oxygen vacancies (OV) and improving PMS activation efficiency. The quantitative structure-activity relationship (QSAR) examination of the intermediates showed a decrease in toxicity, and the potential pathways of ONZ degradation were illustrated using Liquid Chromatography Mass Spectrometry (LC-MS) technology. This work not only demonstrated the effectiveness and stability of Cu-Co-TiO2 as a PMS activator, but it also offered fresh information on how to remove organic pollutants from wastewater by using PMS activation via the radical and non-radical oxidation pathway.