Organic Transformations Research Articles

Hydrazone-Linked Donor-Acceptor Covalent Organic Polymer as a Heterogeneous Photocatalyst for C-S Bond Formation.

In the realm of solar energy utilization, there is a growing focus on designing and implementing effective photocatalytic systems, for the conversion of solar energy into valuable chemical fuels. The potential of Covalent Organic Polymers (COPs) as photocatalysts for visible-light-driven organic transformation has been widely investigated, positioning them as promising candidates in this field. In the design of COPs, introducing a donor-acceptor arrangement facilitates the transfer of electrons from the donor to the acceptor, creating a charge transfer complex and leading to enhanced conductivity and improved charge separation. Here we present a novel hydrazone-linked covalent organic polymer ETBC-PyHz containing TPE donor and pyridine acceptor. Utilizing this, an efficient method has been developed for an oxidative cross-coupling reaction involving C-S bond formation. This process involves arylhydrazines and arenethiols, and results in the production of unsymmetrical diaryl sulfides via the formation of aryl and thioarene radicals. This conversion holds significant importance because the byproducts produced during the process are nitrogen and water, making it environmentally benign.

Di-tert-butyl Peroxide (DTBP)-Promoted Heterocyclic Ring Construction

Abstract: Di-tert-butyl peroxide (DTBP) is one of the most widely used organic peroxides in a variety of oxidative transformations. The main factors contributing to the increasing use of DTBP are its affordability, minimal environmental impact, great effectiveness, and capacity to substitute scarce or dangerous heavy metal oxidants. We have reviewed critically and succinctly the noteworthy applications of DTBP in heterocyclic ring constructions from 2014 onwards in this decennial update. The main components of this evaluation are the pros and cons of its use, the scope of a synthetic organic transformation, and mechanistic logistics.

Long-lived carriers-promoted photocatalytic deuteration of halides with D2O as the deuterium source over Cu doped quantum dots

Deuterium labeling is a highly valuable yet challenging subject of research in various scientific fields. Conventional deuteration methods often involve harsh reaction conditions and suffer from limited reactivity and selectivity. Herein, we report a visible light–driven C–X (X = halogen) to C–D (D = deuterium) exchange strategy over copper-doped cadmium sulfide quantum dots (Cu-CdS QDs) under mild conditions, eliminating the need for noble metal catalysts and expensive deuterium sources. The conversion of aryl halides into deuterated products using Cu-CdS QDs reaches up to 99%, which is four times higher than that achieved using pristine CdS QDs. The substantial enhancement in the photocatalytic activity of the QDs can be primarily attributed to the generation of long-lived charge carriers (approximately 6 μs) induced by Cu doping. Mechanistic studies reveal that the Cu dopants considerably retard the recombination of photoinduced carriers by creating intermediate energy levels that serve as hole trapping centers in CdS QDs, thereby improving the electron utilization efficiency in energetically demanding photoreduction reactions. Additionally, the introduction of Cu increases the energy offset between the conduction band of CdS QDs and molecular acceptors, facilitating the electron transfer process. Upon visible light irradiation, a series of aryl halides can be efficiently converted into the desired deuterated compounds using D2O as the deuterium source. This work demonstrates that regulating charge carrier dynamics in ultrasmall QD-based photocatalysts is a promising strategy for promoting organic transformations.

Iron-Catalyzed Chemoselective Transfer Hydrogenation of α,β-Unsaturated Ketones Using H2O as a Surrogate of Hydrogen.

Sustainable and highly economical iron-catalyzed chemoselective reduction of C═C of α,β-unsaturated ketones has been established under mild reaction protocols. Water is used as a green and abundant surrogate of hydrogen and is scarcely used in organic synthetic transformations as a source of hydrogen. The developed protocol offers a broad spectrum for chemoselective transfer hydrogenation of α,β-unsaturated ketones. Moreover, the method was found to be highly effective for aryl and ferrocenyl α,β-unsaturated ketones consisting of one or two double bonds and with multiple functionalities. Moreover, the present method avoids prolonged reaction time, provides a wide range of substrates with excellent yield, and circumvents the tedious chromatographic workup.

Oxidative Organic Transformations Photocatalyzed by NDI in Visible Light.

In this work, we report the synthesis and photocatalytic properties of N,N-bis(n-hexyl)-2-bromo-6-(n-hexylamino)-1,4,5,8-naphthalenetetracarboxylic diimide photocatalyst, NDI-PC, in visible light. In the presence of air or oxidant, NDI-PC efficiently enables multiple photooxygenations of isoquinolines, thiocyanation of phenylimidazopyridines, functionalization of quinolinones by allowing regioselective installation of an SCN, SeCN, SPh, SePh, Cl, Br, or I group at the C-3 position, and isomerization of alkenes. Mechanistic investigations suggest an oxidative photoredox process for oxygenation and C-H functionalization, while isomerization is believed to proceed through a photosensitization pathway.

Design, Synthesis, and In Vitro Cytotoxic Studies of Some Novel Arylidene-Hydrazinyl-Thiazoles as Anticancer and Apoptosis-Inducing Agents.

Cancer, defined by uncontrolled cell growth, poses a significant global health challenge, necessitating the development of new anticancer drugs crucial to address drug resistance, side effects, and the need for combination therapies. The study presents the design, synthesis, and anticancer screening of a series of novel functionalized arylidene-hydrazinyl-thiazoles against various human cancer cell lines. The environmentally benign synthetic protocol involves the visible-light prompted, NBS-mediated domino reaction of thiosemicarbazide, heteroaryl aldehydes, and unsymmetrical 1,3-diketones. The regioselective organic transformation delivered the single regioisomeric product, characterized unambiguously through detailed 2D NMR spectral studies. In vitro cytotoxic studies revealed that the synthesized derivatives exhibited excellent cytotoxic potential against BxPC-3, MOLT-4, and MCF-7 cancer cell lines. Notably, compounds 4m, 4n, and 4r showed significant cytotoxicity, reducing cell survival to 23.85-26.45% for BxPC-3, 30.08-33.30% for MOLT-4, and 44.40-47.63% for MCF-7 at a concentration of 10 μM. These compounds profoundly induced apoptosis, evidenced by increased caspase-3/7 activity, loss of mitochondrial membrane potential, and modulation of Bcl2 and Bax gene expression. Additionally, these compounds caused robust cell cycle arrest at the G2/M phase by inhibiting tubulin polymerization, indicating their multifaceted impact on cancer cells.

Triplet Energy Transfer (EnT)-Promoted 1,3-Dipolar Cycloaddition Reactions of N-(Trimethylsilyl)methylphthalimide with Electron-Deficient Alkynes and Alkenes.

Triplet energy transfer (EnT)-promoted photochemical pathways, arisen by visible light and its photosensitizers, have gained significant attention as a complementary strategy for initiating organic transformations in photochemical reactions that are unlikely to occur through a single electron transfer (SET) process. In the present study, we investigated the triplet EnT-promoted 1,3-dipolar cycloaddition reactions of N-(trimethylsilyl)methylphthalimide with electron-deficient alkynyl and alkenyl dipolarophiles. The triplet excited state of N-(trimethylsilyl)methylphthalimide, promoted by the triplet EnT from thioxanthone (TXA) photosensitizer, underwent sequential intramolecular SET and carbon-to-oxygen migration of the silyl group to form azomethine ylide. This generated ylide cycloadded to alkynes or alkenes to regioselectively and stereospecifically produce a nitrogen-containing benzopyrrolizidine scaffold with multiple stereogenic centers. Crucially, the stereoselectivity of these cycloaddition reactions (i.e., endo versus exo addition) was influenced by the nature of the dipolarophiles.

Utilization of Diversified Cover Crops as Green Manure-Enhanced Soil Organic Carbon, Nutrient Transformation, Microbial Activity, and Maize Growth

Studying green manure in several returning methods to enhance soil fertility and crop benefits is a strong foundation for cropland nutrient management. However, how different types of green manures and their variable doses affect the efficacy of applied manures, either buried or mulched, remain overlooked. The objective of this study was to optimize green manure management to enhance soil fertility and maize biomass using five types of green manures (white mustard, forest rye, fiddleneck, sufflower, and pea) in two different doses (low, 5 g per pot, and high, 10 g per pot), which were either buried or mulched before and after maize sowing. Results revealed that total carbon content increased due to green manure treatments, representing a 10% increase over control, particularly through buried w. mustard (10% increase before maize cultivation) and mulched safflower and pea (12% and 11% increase after maize cultivation over control). Dry maize aboveground biomass yields also improved across all variants, with buried mustard yielding 18.4 g·plant−1 (compared to 8.6 g·plant−1 in the control), mulched mustard yielding 16.4 g·plant−1, and buried pea yielding 17.8 g·plant−1. Green mulching generally acidified the soil (pH 5.71 compared to 6.21 in the control), except for buried fiddleneck (pH 6.39 after maize cultivation) at a high dose of manures. Carbon-mineralizing enzyme activities (dehydrogenase and β-glucosidase) were significantly increased by green manures, with buried fiddleneck showing a 22.6% and 20.6% increase over the control, and mulched fiddleneck showing a 24.5% and 22.4% increase under high doses. The study suggests that partially decomposed and mineralized mulched biomass may induce a negative priming effect on carbon-mineralizing enzymes due to a decrease in the C/N ratio of the soil. It emphasizes that the nutrient content and stoichiometry of green manures, alongside soil characteristics such as the C/N ratio, are critical factors for sustainable soil management and carbon sequestration. These findings underscore the need for careful selection and management of green manures to optimize soil health and carbon-storage outcomes.

Recent progress in visible light‐driven halogenation: Chlorination, bromination, and iodination

AbstractHalogenation is one of the most important transformations in organic synthesis. Halogenated compounds are employed in many reactions to prepare useful molecules. Many methods have been developed to introduce halogens into different compounds. Visible light‐mediated reactions are the efficient, low‐toxic, and mild‐condition methods applied for various organic chemistry transformations. Remarkably, there has been an increasing development in the application of visible light‐induced halogenation in recent years. Herein, we present a comprehensive summary of halogenation reactions including chlorination, bromination, and iodination under visible light irradiation since 2020.

A Decade of Advancement in Ruthenium (II)-Catalyzed Direct C-H Activation and Consequent C-C/C-N Bond Formation Using Microwave Heating

: Transition-metal catalysed activation of unreactive C-H bonds and subsequent C-C bond formation has emerged as a principal and essential tool in the field of synthetic organic chemistry. On the other hand, the microwave heating technique has been intensively used to carry out organic transformation of almost all kinds and has become a promising non-conventional technique for performing synthetic reactions. Direct C-H activation for C-C bond-forming reactions using ruthe-nium as a catalyst is currently a hot topic and represents a cost-effective synthetic pathway in or-ganic chemistry which is accompanied by the advantages of MW irradiation resulting in shorter reaction time and greener 3 as well as sustainable accomplishments.

Investigation of Structural, Photoelectrochemical, Magnetic and Catalytic Properties of LaSrNiO4, LaSrCuO4, LaSrCoO4 Nanoparticles Synthesised by Reverse Micellar Route

AbstractLaSrCoO4, LaSrNiO4 and LaSrCuO4 were synthesised by the reverse micellar route by using three different microemulsion compositions. The as prepared nanostructures were characterised by powder X‐ray diffraction (PXRD), field emission scanning electron microscopy, energy dispersive X‐ray spectroscopy and transmission electron microscopy. The PXRD of all samples indicate pure phases which crystallize into a tetragonal system. The particle size and shape of nanoparticles varies with microemulsion system. Magnetisation studies suggested that two of the LaSrCoO4 samples display canted antiferromagnetism while the others showed no sign of long‐range ordering. The LaSrNiO4 and LaSrCuO4 samples seemed to show spin glass behaviour. Some of these materials were successfully used as catalysts for organic transformations. The esterification of aldehydes in the presence of alkyl halides and alcohols has been made mild and practicable with a copper catalysed TBHP/DTBP promoting reaction. This approach is suitable to a wide variety of aldehydes, including those that are notoriously difficult to convert through the C(sp2)−H bond scission to produce the required esters in good to outstanding yield.

Visible‐Light Photocatalytic Cyclopropanation of Alkenes with Dibromomethane

AbstractThe cyclopropane unit plays a crucial role in pharmaceutical compound design and organic transformation. In this study, we have developed a novel redox‐neutral photocatalytic cyclopropanation method involving dibromomethane and alkenes. This chemistry enables the synthesis of valuable functional group‐substituted cyclopropanes using readily available starting materials and practical reaction conditions. Additionally, we have demonstrated the versatility of the products as precursors for various cyclopropane derivatives with different substituents. Importantly, this protocol facilitates the synthesis of a key unit found in a specific type of T‐type calcium channel blocker. Furthermore, the proposed reaction mechanism is well‐supported by control experiments.

Highly active nitrogen-doped biochar for catalytic reduction of 4-nitrophenol: Kinetic, thermodynamic and mechanism investigation

Biomass derived metal-free carbon catalysts are urgently needed in wastewater remediation and organic transformation, due to their environmental friendliness, low cost. In this respect, a series of nitrogen-doped hierarchically porous carbons (NHPCs) derived from cheap and abundant eggplant were fabricated via a one-pot strategy under different temperatures from 600 to 900°C, and employed as metal-free catalysts for the reduction of aromatic nitrophenols. Benefiting from the synergistic effects of the hierarchically porous structure, large specific surface area and abundant structural defects, NHPCs obtained from 800 °C has the highest reduction rate of 2.072 min−1 and maximal turnover frequency (TOF) for 4-nitrophenol of 1.23 × 10−2 mM·mg−1·min−1, which is superior to most of the reported metal-free catalysts. In addition, the NHPC-800 also exhibits satisfactory practicality and universality. The kinetic and thermodynamic studies were also conducted, finding that the obtained kinetics data over NHPC-800 fit well to L-H model with a low apparent activation energy (Ea = 18.96 kJ·mol−1). Furthermore, the mechanism was also elucidated by experimental investigation and theoretical calculations, which revealed that the pore creation and doping nitrogen can promote the adsorption of 4-NP and NaBH4 onto NHPC. This study make a significant contribution to the advancement of catalytic reduction of 4-NP by N-doped biochar catalysts.

Recent Advances in Nano Silver Catalysis for Organic Transformations

Recent Advances in Nano Silver Catalysis for Organic Transformations

Disruptive effects of sewage intrusion into drinking water: Microbial succession and organic transformation at molecular level

Drinking water distribution systems are increasingly vulnerable to sewage intrusion due to aging water infrastructure and intensifying water stress. While the health risks associated with sewage intrusion have been extensively studied, little is known about the impacts of intruded bacteria and dissolved organic matter (DOM) on microbiology in drinking water. In this dynamic study, we demonstrate that the intrusion of 1 % sewage into tap water resulted in immediate contamination, including an 8-fold increase in biomass (TCC), a 48.9 % increase in bacterial species (ASVs), a 12.5 % increase in organic carbon content (DOC), and a 13.5 % increase in unique DOM molecular formulae. Over time, sewage intrusion altered tap water microbiology by accelerating bacterial growth rates (5-fold faster), selectively promoting ASVs in community succession, and producing 998 more unique DOM formulae. More significantly, statistical analysis revealed that the intrusion of 1 % sewage shifted the driving force of bacterial and DOM composition covariance from a DOM-dependent process in tap water to a bacterial-governed process post-intrusion. Our results clearly demonstrate the disruptive effects of sewage intrusion into tap water, emphasizing the urgent need to consider the long-lasting impacts of sewage intrusion in drinking water distribution systems, in addition to its immediate health risks.

Rational design of the substrate binding pocket in epoxide hydrolase for enhanced enantioselectivity towards chiral ortho-methylstyrene oxide

Epoxide hydrolases are crucial enzymes for the stereospecific hydrolysis of racemic epoxides, serving as biocatalysts for synthesizing optically pure epoxides. The (S)-ortho-methylstyrene oxide (oMSO) is a valuable chiral building block in asymmetric organic transformations. Our lab previously elucidated the crystal structure of AuEH2, an epoxide hydrolase from Aspergillus usamii. Here, we conducted saturation mutagenesis on hotspots in the AuEH2 substrate binding pocket (SBP), creating a library of 181 single-site mutations. Screening with rac-oMSO revealed a mutational landscape of enzymatic activity and E value. Using an innovative sequence-activity relationship (innov'SAR) machine learning approach, a double mutant AuEH2A214V/S247Q was identified with obviously improvements enantiomeric ratio (E value= 28.3) for (R)-oMSO that was increased 7.9-fold over wild type. Using E. coli/Aueh2A214V/S247Q at 10 mg/mL, we dynamically resolved 20 mmol/L rac-oMSO at 25 °C, yielding (S)-oMSO with 96.7 % ees and 1,2-diol (R)-oMPED with 81.0 % eep. Molecular dynamics (MD) simulations indicated that changes in SBP residue interactions and non-covalent interactions with (R)-oMSO contributed to the increased activity and enantioselectivity of AuEH2A214V/S247Q.

Distribution and Genesis of Aliphatic Hydrocarbons in Bottom Sediments of Coastal Water Areas of the Crimea (the Black and Azov Seas)

The aim of the article is to assess the level of aliphatic hydrocarbon (AHC) contamination in bottom sediments of the Azov–Black Sea coast of the Crimea, as well as to identify potential sources of its formation. Bottom sediment samples obtained from 19 stations during the research cruise of the R/V “Professor Vodyanitsky” (June 2020) were used as the material for this investigation. Sampling stations were located along the coast of the Crimean Peninsula and the Caucasus coastlines (the Black and Azov Seas). N-hexane extracts of sediments were studied by gas chromatography to determine the AHC amount and composition. It was established that AHC concentrations in the study area varied from 1.30 to 127.8 mg/100 g. Generally, bottom sediments of the Black and Azov Seas were characterized by low AHC contents, while increased AHC contents were found in the outer harbor of Sevastopol and Yalta regions. To identify potential hydrocarbon sources, various hydrocarbon markers were used. In most of the study areas, n-alkane composition was determined by similar sources of inputs and organic compound transformation. At the same time, oil pollution linked with use of fuel was recorded almost everywhere.

Insights into relationship between microbial community-induced polycyclic aromatic hydrocarbons degradation and soluble organic matter transformation during vermiculite-amended sewage sludge composting

Vermiculite is a natural clay mineral with unique properties that are widely used in plant cultivation, soil remediation, and solid waste management. This study investigated the relationship between microbial community-induced polycyclic aromatic hydrocarbons (PAHs) degradation and dissolved organic matter (DOM) transformation during vermiculite-amended composting of sewage sludge. Four treatments with varying vermiculite percent compositions, 0%, 1%, 5%, and 10%, mixed with initial mix waste, were designed and then composted for 33 days. The results showed that the addition of 1% vermiculite caused the highest losses of 82.19%, 52.98%, and 69.00% for LMW-PAHs (2–3 rings), HMW-PAHs (4–6 rings), and total PAHs respectively compared to other treatments. Spectral and community analyses revealed that 1% vermiculite enhanced the PAHs losses by functional networking of key genera and promoting the aromatization and humification of DOM to format the micelles with PAHs. The transformation and utilization of DOM driven by key genera Acinetobacter, Ochrobactrum, Pseudoxanthomonas, and Bacillus were the important impact factors for the losses of PAHs. Finally, this study provides new insights and a guide for applying vermiculite to sludge composting for PAHs removal.

Some New Aspects of Gold-Catalyzed Benzannulation Reaction

Introduction: The gold-catalyzed benzannulation reaction of oxo-alkynes with al-kenes or alkynes is one of the important and unique reactions in gold-catalyzed organic trans-formations. Methods: In this manuscript, many facets of this reaction have been discussed concerning reac-tivity and selectivity, along with a new self-benzannulation process. The scope of this chemistry was extended to construct a phenanthrene moiety. Results: In addition, a palladium-gold dual catalytic arylation of isobenzopyrylium salts using arene-diazonium salts as an aryl group source and a one-pot isoquinoline synthesis is reported for the first time. Conclusion: Moreover, a conductance measurement experiment was performed, which supports the formation of ionic species, most likely the isobenzopyrylium auric ate complex as an inter-mediate formed during the reaction process.

Green Molecular Reactor Boosting the Photocatalytic Aerobic Oxidation of Sulfides in Clean Solvent

AbstractThe 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.