Organic Reactions Research Articles

Halogen Bond Catalysis: A Physical Chemistry Perspective.

As important noncovalent interactions, halogen bonds have been widely used in material science, supramolecular chemistry, medicinal chemistry, organocatalysis, and other fields. In the past 15 years, halogen bond catalysis has become a developed field in organocatalysis for the catalysts' advantages of being environmentally friendly, inexpensive, and recyclable. Halogen bonds can induce various organic reactions, and halogen bond catalysis has become a powerful alternative to the fully explored hydrogen bond catalysis. From a physical chemistry view, this perspective provides an overview of the latest progress and key examples of halogen bond catalysis via activation of the lone pair systems of organic functional group, π systems, and metal complexes. The research progresses in halogen bond catalysis by our group were also introduced.

In Operando Visualization of Elementary Turnovers in Photocatalytic Organic Synthesis.

We report the in operando visualization of the photocatalytic turnovers on single eosin Y (EY) through a redox-induced photoblinking phenomenon. The photocatalytic cyclization of thiobenzamide (TB) catalyzed by EY was investigated. The analysis of the intensity-versus-time trajectories of single EYs revealed the kinetics and dynamics of the elementary photocatalytic turnovers and the heterogeneity of the activity of individual EYs. The quenching turnover time showed a fast population and a slow population, which could be attributed to the singlet and triplet states of photoexcited EY. The slow quenching turnovers were more dominant at higher TB concentrations. The activity heterogeneity of EYs was studied over a series of reactant concentrations. Excess quenching reagent was found to decrease the percentage of active EYs. The method can be broadly applied to studying the elementary processes of photocatalytic organic reactions in operando.

Nitrogen-doped Carbon Dots as Efficient Photocatalysts for High Selectivity of Dehalogenative Oxyalkylation of Styrene.

Carbon dots (CDs) are a type of carbon-based luminescent material with a zero-dimensional structure and a size of less than 10 nm, which are composed of sp2/sp3 hybrid carbon nuclei and surface functional groups. Because CDs has strong photoluminescence and good light absorption in the ultraviolet and near visible regions, it is an excellent candidate for photocatalytic applications. However, the use of nonmetallic doped CDs as photosensitizers for direct photocatalytic organic reactions has been limited to several scattered reports. Herein, we present nitrogen-doped carbon dots (N-CDs) that has a capability for not only produce reactive oxygen species (ROS), including superoxide anion radical (O2⋅-) and singlet oxygen (1O2), but also provide an unprecedented high activity of dehalogenative oxyalkylation of styrene with a yield of 93 %. This work develops a novel opportunity to utilize cost-effective and easily accessible CDs for the advancement of photocatalysis.

Self-propelled assembly of nanoparticles with self-catalytic regulation for tumour-specific imaging and therapy

Targeted assembly of nanoparticles in biological systems holds great promise for disease-specific imaging and therapy. However, the current manipulation of nanoparticle dynamics is primarily limited to organic pericyclic reactions, which necessitate the introduction of synthetic functional groups as bioorthogonal handles on the nanoparticles, leading to complex and laborious design processes. Here, we report the synthesis of tyrosine (Tyr)-modified peptides-capped iodine (I) doped CuS nanoparticles (CuS-I@P1 NPs) as self-catalytic building blocks that undergo self-propelled assembly inside tumour cells via Tyr-Tyr condensation reactions catalyzed by the nanoparticles themselves. Upon cellular internalization, the CuS-I@P1 NPs undergo furin-guided condensation reactions, leading to the formation of CuS-I nanoparticle assemblies through dityrosine bond. The tumour-specific furin-instructed intracellular assembly of CuS-I NPs exhibits activatable dual-modal imaging capability and enhanced photothermal effect, enabling highly efficient imaging and therapy of tumours. The robust nanoparticle self-catalysis-regulated in situ assembly, facilitated by natural handles, offers the advantages of convenient fabrication, high reaction specificity, and biocompatibility, representing a generalizable strategy for target-specific activatable biomedical imaging and therapy.

Impact of Prompt Cueing on Level of Explanation Sophistication for Organic Reaction Mechanisms

Impact of Prompt Cueing on Level of Explanation Sophistication for Organic Reaction Mechanisms

Transition metal modified Al2O3 mesoporous nanospheres for catalysis of organic reactions

The performance of metal oxide-based catalysts are usually determined by their characteristics such as material composition, morphology, and surface/interface properties. Therefore, rational design of metal oxide-based catalysts with special surface/interface characteristics and porous microstructure still needs further research. In this work, a facile two-step solvothermal-annealing method is developed for the synthesis of transition metal (TM) modified Al2O3 (TM-Al2O3, TM = Cu, Fe, Ni, Co) nanospheres. The influences of different ratios of solvents (e.g., water and glycerol) on the morphology and particle size of the nanocatalysts are explored. Benefitting from the nano-spherical morphology and unique mesoporous structure, the representative catalyst (i.e., Cu-Al2O3) exhibits favorable catalytic performance in 4-nitrophenol reduction and benzyl alcohol oxidization reactions. The turnover frequency of Cu-Al2O3 is high up to 35.9 min−1 for the reduction of 4-nitrophenol, which is higher than that of its counterparts (i.e., Fe-Al2O3, Ni-Al2O3, and Ni-Al2O3) and many recently reported Al2O3-based catalysts. Moreover, the pH of the reaction system is regulated to enhance the catalytic efficiency in selective oxidization of benzyl alcohol by an additive addition strategy. These results suggest that the nano-spherical and mesoporous morphology is indeed effective for the activity enhancement of TM-Al2O3 catalysts. The same catalyst designing concept and performance regulation strategy may be extended to other TM-modified metal oxide systems, making it possible to tune the catalytic behavior for various chemical reactions.

Supramolecular immobilization of lipase inspired by octopus suckers for biodiesel production

It is still a challenge to design a supramolecular interaction system for immobilizing enzymes efficiently and stably. In this work, inspired by octopus suckers, we used cyclodextrin with a similar structure to the octopus sucker cavity as supramolecular interaction functional units of soft tentacles to immobilize lipase through physical adsorption. By modifying the surface of cyclodextrin with polar hydrophilic groups, the difference in hydrophilic and hydrophobic properties and stability within the molecule were effectively improved, thereby enhancing the cavity suction of cyclodextrin. The enzyme load of the soft tentacles reached 10 mg/g, and the lipase was adsorbed firmly under high strength mechanical action (the retention rate is 66.4%, other physical adsorption under the same conditions is 51.6%). The soft tentacle immobilized lipase showed good dispersibility in the organic phase and its water absorption characteristics could provide oil-water interface for lipase in organic phase reaction, promoting the forward transesterification reaction. Compared with free lipase, the soft tentacle immobilized lipase (L-CDST-Ms) showed the improved activity, which could reach 180% of that of free lipase. The L-CDST-Ms was applied to biodiesel production, and the conversion rate could reach 94%. The results showed that the immobilization method opened up a new way for the application of lipase in transesterification.

Active metals decorated NiCo2O4 yolk-shell nanospheres as nanoreactors for catalytic reduction of nitroarenes and azo dyes

Transition-metal oxides (TMOs) have received a great deal of research attention and have been widely used in a variety of fields. However, conventional TMOs do not possess high specific surface area, sufficient active site on their surfaces, and limited their applications in catalysis. This study presents a two-step method for synthesizing active metal (M) decorated NiCo2O4 (M/NiCo2O4, M = Pd or Cu) nanospheres with yolk-shell nanostructures. Taking advantage of the unique morphology and the combination of dual active components (i.e., active NiCo2O4 substrate and decorated active metal), the as-prepared M/NiCo2O4 yolk-shell nanospheres can be employed as nanoreactors in the organic reactions. In catalyzing the reduction of a representative nitroarene (i.e., 4-NP) by NaBH4, the Pd/NiCo2O4 nanoreactors exhibit a superior catalytic efficiency to their counterparts (Cu/NiCo2O4 and NiCo2O4). The turnover frequency is much higher than that of various TMOs supported nanocatalysts have been reported over the past five years. Furthermore, the Pd/NiCo2O4 nanoreactors show excellent stability and common applicability of the reduction of various substituted nitrobenzenes and azo dyes. This work provides new rational design concept and preparation strategy for efficient nanoreactors with dual active components and sheds light on the practical application of chemical reactions.

Metal Complexes for Dye-Sensitized Photoelectrochemical Cells (DSPECs).

Since Mallouk's earliest contribution, dye-sensitized photoelectrochemical cells (DSPECs) have emerged as a promising class of photoelectrochemical devices capable of storing solar light into chemical bonds. This review primarily focuses on metal complexes outlining stabilization strategies and applications. The ubiquity and safety of water have made its splitting an extensively studied reaction; here, we present some examples from the outset to recent advancements. Additionally, alternative oxidative pathways like HX splitting and organic reactions mediated by a redox shuttle are discussed.

One-Flow Operation via 4-Bromopyridine Enables Flash Synthesis of AChE Inhibitor

Abstract4-Bromopyridine is a building block that can be converted into valuable compounds, but due to its low stability, it is commercially available in the form of hydrochloride salt. Therefore, the hydrochloride salt is usually desalted with a basic aqueous solution and dried before organic reaction. In this study, to simplify the preparation and reaction procedure of 4-bromopyridine, multiple operations, desalting with a base, separation of the aqueous layer, and subsequent halogen–lithium exchange reaction were integrated into a single flow reaction. The reaction sequence was completed within 20 seconds and the yields were higher than the conventional methods. This is because the subsequent reaction can be performed immediately after the generation of 4-bromopyridine, which is unstable under ambient conditions.

Aerobic Catalytic Cross-Dehydrogenative Coupling of Furans with Indoles Provides Access to Fluorophores with Large Stokes Shift.

Sustainability in chemical processes is a crucial aspect in contemporary chemistry with sustainable catalysis as a vital parameter of the same. There has been a renewed focus on utilizing earth-abundant metal catalysts to expand the repertoire of organic reactions. Furan is a versatile heterocycle of natural origin used for multiple applications. However, it has scarcely been used in cross-dehydrogenative coupling. In this work, we have explored the cross-dehydrogentive coupling of furans with indoles using commonly available, inexpensive FeCl3 ⋅ 6H2 O (<0.25 $/g) as catalyst in the presence of so called 'ultimate oxidant' - oxygen, without the need for any external ligand or additive. The reactions were found to be scalable and to work even under partially aqueous conditions. This makes the reaction highly economical, practical, operationally simple and sustainable. The methodology provides direct access to π-conjugated short oligomers consisting of furan, thiophene and indole. These compounds were found to show interesting fluorescence properties with remarkably large Stokes shift (up to 205 nm). Mechanistic investigations reveal that the reaction proceeds through chemoselective oxidation of indole by the metal catalyst followed by nucleophilic trapping by furan.

Persistent intracranial hyper-inflammation in ruptured cerebral aneurysm after COVID-19: case report and review of the literature

BackgroundThe systemic manifestations of coronavirus disease 2019 (COVID-19) include hyperinflammatory reactions in various organs. Recent studies showed evidence for the frequent involvement of central nervous system in affected patients; however, little is known about clinical features of cerebrovascular diseases in childhood-onset COVID-19.Case presentationA 10-year-old boy recovered from SARS-CoV-2 infection without complication. On 14 days after infection, he presented with loss of consciousness. A head computed tomography detected a ruptured cerebral aneurysm at the left posterior cerebral artery accompanying subarachnoid hemorrhage (SAH). Immediate surgical intervention did not rescue the patient, resulting in the demise 7 days after admission. Serological and genetic tests excluded the diagnosis of vasculitis and connective tissue disorders. Retrospective analysis showed markedly higher levels of interleukin (IL)-1β, IL-6 and IL-8 in the cerebrospinal fluid than the serum sample concurrently obtained. A review of literature indicated that adult patients with COVID-19 have a risk for the later development of SAH during the convalescent phase of COVID-19.ConclusionsSAH is a severe complication of COVID-19 in children and adults who have asymptomatic cerebrovascular aneurysms. The markedly high levels of cytokines detected in the cerebrospinal fluid suggested that intracranial hyperinflammatory condition might be one of the possible mechanisms involved in the rupture of a preexisting cerebrovascular aneurysms.

Recent advances in organic molecule reactions on metal surfaces.

Chemical reactions of organic molecules on metal surfaces have been intensively investigated in the past decades, where metals play the role of catalysts in many cases. In this review, first, we summarize recent works on spatial molecules, small H2O, O2, CO, CO2 molecules, and the molecules carrying silicon groups as the new trends of molecular candidates for on-surface chemistry applications. Then, we introduce spectroscopy and DFT study advances in on-surface reactions. Especially, in situ spectroscopy technologies, such as electron spectroscopy, force spectroscopy, X-ray photoemission spectroscopy, STM-induced luminescence, tip-enhanced Raman spectroscopy, temperature-programmed desorption spectroscopy, and infrared reflection adsorption spectroscopy, are important to confirm the occurrence of organic reactions and analyze the products. To understand the underlying mechanism, the DFT study provides detailed information about reaction pathways, conformational evolution, and organometallic intermediates. Usually, STM/nc-AFM topological images, in situ spectroscopy data, and DFT studies are combined to describe the mechanism behind on-surface organic reactions.

Ionic liquids as a shuttle for releasing and capturing hydrogen chloride: a new way to utilize waste HCl generated in organic reactions

An ionic liquid, 1-[1-(ethoxycarbonyl)-2-oxopropyl]-3-methylimidazolium chloride, was used as a shuttle to release and capture hydrogen chloride, enabling waste HCl to be used in organic reactions.

Recent trends for chemoselectivity modulation in one-pot organic transformations.

In organic reactions, chemoselectivity refers to the selective reactivity of one functional group in the presence of another. This can be more successful if the reagent and reaction parameters are appropriately chosen. One-pot reactions have been shown to be an effective structural variety technique for the development of novel heterocyclic or carbocyclic compounds. This review article focuses on recent efforts by researchers from around the world to synthesise novel organic molecules utilising these methodologies (2013-2024), as well as their mechanism insights. The substrate, catalyst, solvent, and temperature conditions all have a significant impact on chemoselectivity in the organic reactions described here. The manipulation of chemoselectivity in organic processes creates new potential for the production of novel heterocycles and carbocycles.

Synthesis and study of antibiofilm and antivirulence properties of flavonol analogues generated by palladium catalyzed ligand free Suzuki-Miyaura coupling against Pseudomonas aeruginosa PAO1.

The Suzuki-Miyaura coupling is one of the ubiquitous method for the carbon-carbon bond-forming reactions in organic chemistry. Its popularity is due to its ability to undergo extensive coupling reactions to generate a broad range of biaryl motifs in a straightforward manner displaying a high level of functional group tolerance. A convenient and efficient synthetic route to arylate different substituted flavonols through the Suzuki-Miyaura cross-coupling reaction has been explained in this study. The arylated products were acquired by the coupling of a variety of aryl boronic acids with flavonols under Pd(OAc)2 catalyzed reaction conditions in a ligand-free reaction strategy. Subsequently, the antibiofilm and antivirulence properties of the arylated flavonols against Pseudomonas aeruginosa PAO1 were studied thoroughly. The best ligands for quorum sensing proteins LasR, RhlR, and PqsR were identified using molecular docking study. These best fitting ligands were then studied for their impact on gene expression level of P. aeruginosa by RT-PCR towards quorum sensing genes lasB, rhlA, and pqsE. The downregulation in the gene expression with the effect of synthesized flavonols endorse the antibiofilm efficiency of the compounds.

OBTENÇÃO DE AMINAS PRIMÁRIAS A PARTIR DA REDUÇÃO DE NITROCOMPOSTOS AROMÁTICOS VIA PROTOCOLOS DE REAÇÕES SUSTENTÁVEIS PARTE II: EM MEIO ORGÂNICO

SYNTHESIS OF PRIMARY AMINES FROM THE REDUCTION OF AROMATIC NITRO COMPOUNDS THROUGH SUSTAINABLE REACTION PROTOCOLS PART II: REACTIONS IN ORGANIC MEDIA. The reduction of nitroarenes is the main methodology to produce anilines, important precursors of building blocks, dyes, and drugs. Continuing our goal of describing sustainable methodologies for the reduction of nitroarenes to their respective anilines, herein we compile selected reaction protocols, using organic medium, reported from 2017 to 2023, in order to provide a comprehensive and complementary view of the new processes and catalysts developed during this period.

Transition metal-catalyzed transformations of 2-formylarylboronic acids.

2-Formylarylboronic acids are easily available precursors in organic chemistry. Different types of transition metal catalysts, such as Pd(0), Pd(II), Rh(I), Ir(I), Ni(II), Cu(I), Cu(II), and Co(II), can efficiently catalyze coupling reactions of 2-formylarylboronic acids with other organic reactants. In this review, we describe the synthesis of a diverse range of carbocyclic and heterocyclic compounds, as well as acyclic compounds, via transition metal-catalyzed reactions of 2-formylarylboronic acids over the past two decades.

Unravelling the underlying mechanism of the reduction of aldehydes/ketones with metal borohydride in an aprotic solvent.

The reduction mechanism of aldehyde/ketones with M(BH4)n is not fully understood, even though the hydroboration mechanism of weak Lewis base borane complexes is known to involve a four-membered ring transition state. Herein, the reduction mechanism of M(BH4)n in aprotic solvents has been elucidated for a six-membered ring, in which hydride transfer to the C atom from the B atom, formation of an L·BH3 adduct, and disproportionation of (BH3(OR)-) borane are involved. The metal cations and solvents participate in and significantly influence the reaction procedure. We believe that this mechanistic study would provide a further reference for the application of M(BH4)n in organic reactions.

3-(Sulfamic acid)-propyltriethoxysilane on biochar nanoparticles as a practical, biocompatible, recyclable and chemoselective nanocatalyst in organic reactions.

Recyclable and inexpensive catalysts, waste regeneration, use of available and safe solvents are important principles of green chemistry. Therefore, in this project, biochar nanoparticles (BNPs) were synthesized by the pyrolysis method from chicken manure. Then, 3-(sulfamic acid)-propyltriethoxysilane (SAPES) was immobilized on the surface of BNPs (SAPES@BNPs). The prepared catalyst (SAPES@BNPs) was used as a commercial, practical, biocompatible and reusable catalyst in the selective oxidation of sulfides to sulfoxides. Further, the catalytic application of SAPES@BNPs was explored in the multicomponent synthesis of tetrahydrobenzo[b]pyrans under mild and green conditions. BNPs were characterized using SEM, TGA and XRD techniques. SAPES@BNPs were characterized using SEM, FT-IR spectroscopy, WDX, EDS, TGA, and XRD techniques. Particle size distribution was obtained by histogram graph. SAPES@BNPs can be recovered and reused several times. The purity of the products was studied using NMR spectroscopy.