Stereoselective Research Articles

Deciphering the mass transfer and diffusion behavior in the oxidation of fatty alcohols to fatty acids over Pt/MCM-41

Selective oxidation of long-chain fatty alcohols into acids is an important value-added reaction. However, exploring the basic catalytic steps over Pt-based catalysts throughout the entire oxidation process is still ambiguous. In this work, we systematically investigated the synergistic mechanisms of adsorption, reaction, and diffusion over Pt/MCM-41 for normal/isomeric alcohols oxidation into acids via molecular dynamics, in-situ characterization, and experiments. Specifically, diffusion coefficients decrease with the increase of the molecular weight of normal molecules due to the increased van der Waals forces, while isomeric alcohols exhibit more complex patterns originated from the steric hindrance between Pt particles and mesopores. To quantitatively describe this pattern, a cluster size descriptor of dPt0.75×dPore0.25 was defined. Notably, 2-ethylhexanol exhibits the best self-diffusion coefficients at the descriptor value of 3.14. Correspondingly, the oxidation of 2-ethylhexanol to 2-ethylhexanoic acid displays highest reaction conversion (68.67 %) and selectivity (65.59 %).

The MoS2/rGO embed in macro-porous PAN gel as a novel DGT binding phase for the rapid and accurate detection of trace Hg(II)

The development of binding gels with a fast uptake rate, high capacity, and good selectivity could be beneficial for trace Hg(II) detection based on the DGT technology. In this study, a novel PAN@MoS2/rGO-DGT was assembled by using the nanocomposite embedded in polyacrylonitrile membrane (PAN@MoS2/rGO) as the binding phase. The interior regular finger-like macropore of the gel provided a convenient channel for the rapid mass diffusion of Hg(II), and the abundant sulfur offered the paramount driving force for trapping Hg(II). These endowed the PAN@MoS2/rGO with an impressive reaction rate, capacity, and selectivity toward Hg(II) and featured the PAN@MoS2/rGO-DGT with excellent diffusion rate (D) and adaptability in the complex matrixes across a wide range of pH, ion strength, common cations. However, the uptake of Hg(II) was influenced by the high content of chloride, thus a calibrated model was established based on the chloride concentration to correct the accumulated mass and D. After that, the high accuracy of this method was confirmed through the good consistency between Hg(II) concentration assessed by DGT and in bulk solution when the DGT was deployed to the river water, seawater, and domestic wastewater at the static and dynamic Hg(II) concentration. Field trials in the prawn farming seawater and lake water also showed a negligible deviation of Hg(II) content from the DGT and the conventional method, acquiring the actual Hg(II) level as 1.07-3.69 ng/L. The findings highlighted the application potential of macropore PAN gel hybrid with nanocomposite as a promising binding phase for trace Hg(II) or other pollutant detection.

Interfacial engineering to create ionically bonded heterostructures for ampere-level chlorine-free anodic reactions in seawater

Production of hydrogen directly from seawater can be a sustainable method; however, corrosive and competitive chlorine chemistry at the anode interfere with the oxygen evolution reaction (OER). Special materials need to be designed to avoid chlorine chemistry; hence, a two-dimensional metal-organic framework@WO3.B2O3 (MOF@WB) heterostructure with ionic bonds was engineered, which can deliver ~10x better performance and is ~65% more economical than commercial IrO2 for OER. Our system is stable in alkaline seawater for over 1000h without chlorine evolution and remains functional even after sitting idle for 5 days, making it integrable with renewable power sources. The catalyst also operated stably at the industrial-scale current density of 1.58Acm-2 for over 100h with 99% performance retention in alkaline seawater. Theoretical calculations reveal that B assists in the adsorption of the MOF on the WO3 substrate via the creation of ionic bonds, resulting in optimized surface geometries for selective reactions, which safeguard against chlorine chemistry. B2O3 helps modulate the B-OH sites at the interface via B-O-B bond hydrolysis, activating the OER kinetics, hence providing an ideal platform for effective direct seawater catalysis to produce low-cost hydrogen.

Dynamically Stabilizing Oxygen Atoms in Silver Catalyst for Highly Selective and Durable CO2 Reduction Reaction

AbstractOxide derived catalyst displays outstanding catalytic activity and selectivity in electrochemical carbon dioxide reduction reaction (CO2RR), in which, it is found that residue oxygen atoms play a pivotal role in regulating the catalyst's electronic structure and thus the CO2RR process. Unfortunately, the intrinsic thermodynamic instability of oxygen atoms in oxide derived catalyst under cathodic CO2RR potentials makes it unstable during continuous electrolysis, greatly hindering its practical industrial applications. In this work, we develop a pulsed‐bias technique that is able to dynamically stabilize the residue oxygen atoms in oxide derived catalyst during electrochemical CO2RR. As a result, the oxide derived catalyst under pulsed bias exhibits super catalytic stability in catalyzing electrochemical CO2RR, while keeping excellent catalytic activity and selectivity.

Impact of Side Chains in 1-n-Alkylimidazolium Ionomers on Cu-Catalyzed Electrochemical CO2 Reduction.

This study presents the impact of the side chains in 1-n-alkylimidazolium ionomers with varying side chain lengths (CnH2n+1 where n = 1, 4, 10, 16) on Cu-catalyzed electrochemical CO2 reduction reaction (CO2RR). Longer side chains suppress the H2 and CH4 formation, with the n-hexadecyl ionomer (n = 16) showing the greatest reduction in kinetics by up to 56.5% and 60.0%, respectively. On the other hand, C2H4 production demonstrates optimal Faradaic efficiency with the n-decyl ionomer (n = 10), a substantial increase of 59.9% compared to its methyl analog (n = 1). Through a combination of density functional theory calculations and material characterization, it is revealed that the engineering of the side chains effectively modulates the thermodynamic stability of key intermediates, thus influencing the selectivity of both CO2RR and hydrogen evolution reaction. Moreover, ionomer engineering enables industrially relevant partial current density of -209.5 mA cm-2 and a Faradaic efficiency of 52.4% for C2H4 production at 3.95 V, even with a moderately active Cu catalyst, outperforming previous benchmarks and allowing for further improvement through catalyst engineering. This study underscores the critical role of ionomers in CO2RR, providing insights into their optimal design for sustainable chemicalsynthesis.

Designing persimmon-liked FeOOH-(CrCo)Ox on the plasma-treated cobalt foam for a highly efficient oxygen evolution in an alkaline-seawater electrolyte

Widespread use of high-purity water for hydrogen production in the electrocatalysis field may intensify the shortage of freshwater resource. Although the seawater is abundant, its practical application still faces many challenges due to the adverse chlorine ion reactions and severe corrosiveness, which leads to a low selectivity and poor stability of the anodic oxygen evolution reaction (OER). Herein, the persimmon-like iron-chromium-cobalt metal oxides (FeOOH-(CrCo)Ox) is in-situ engineered on the Co foam surface modified by the dielectric barrier discharge (DBD) plasma (PCF). The obtained FeOOH-(CrCo)Ox/PCF exposes a large specific surface area and rich heterojunction interfaces. Therefore, the optimized electronic structure of FeOOH-(CrCo)Ox/PCF achieves a commercial-grade current density of 1000 mA cm−2 (j1000) with only a overpotential of 348 mV in 1 M KOH, as well as 306 mV for delivering j100 in a harsh alkaline seawater. Additionally, the FeOOH-(CrCo)Ox/PCF also demonstrates an excellent electrocatalytic stability for effectively inhibiting the chlorine corrosion, and only 5.2 % and 17.5 % activity decay occur after 250 h I-t tests with high current densities in 1 M KOH and alkaline seawater, respectively. Furthermore, the DFT results disclose that the synergistic effect between Fe and Co oxides causes a remarkable OER performance, and the Co sites at the FeOOH-CoO interface acts as the main active centers for seawater splitting, promoting the O2 generation effectively.

Selective Cross-Metathesis Versus Ring-Closing Metathesis of Terpenes, Taking the Path Less Travelled.

A diiodo ruthenium olefin metathesis pre-catalyst was employed to achieve remarkably selective cross-metathesis reactions of prenylated 1,6-dienes, effectively overcoming the entropically favored intramolecular ring-closing metathesis. This reaction was investigated using Density Functional Theory (DFT) computations and fine-tuned through the application of a Design of Experiments (DoE) approach. The potential of this innovative process was demonstrated through the unprecedented functionalization of various terpene natural products via cross-metathesis, resulting in the synthesis of new derivatives in a single step.

Single-Site Pd Regulated by π-π Stacking for High-Selectivity Cyclopropanation Reaction.

Cyclopropane-based high-energy fuels possess high intramolecular energy and density, and their precise synthesis is a critical challenge. However, owing to the highest strain in the cyclopropane structure (compared to other four- or five-membered rings, etc.), metal-carbene intermediates form with difficulty, resulting in poor catalytic selectivity for its synthesis. Herein, through rational design of π-π stacking between the Pd organic complex and graphene, we report a single-site Pd catalyst for precise synthesis of multicyclopropane-based high-energy fuels. It is discovered that π-π stacking enhanced the electrophilicity of Pd through a weak metal-support interaction, thus promoting the formation of Pd═C carbene active intermediates. Meanwhile, the adsorption between the active centers and intermediates was enhanced via π-π stacking. These two respects led to almost twice selectivity for cyclopropanation reaction up to 80.5% as that without π-π stacking. This work provides an effective strategy of π-π noncovalent interactions for regulating C-C coupling reaction selectivity.

Pd-Catalyzed Hydrocyanation of Methylenecyclopropanes: A Highly Selective Ring-Opening Access to 2-Substituted Allylic Nitriles.

Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes presents a useful but challenging transformation due to the complex selectivity and multiple reaction pathways. We describe herein an unprecedented highly efficient and selective palladium-catalyzed hydrocyanation of methylenecyclopropanes to give various 2-substituted allylic nitriles. Mechanistic studies demonstrated that the transformation may undergo Markovnikov-type hydrometalation and β-carbon elimination.

Advancements in Inverse-Electron-Demand Diels–Alder Cycloaddition of 2-Pyrones: Mechanisms, Methodologies

The Diels-Alder (DA) cycloaddition is well-known for its effectiveness in synthesizing natural products and multifunctional materials. This article specifically explores the inverse-electron-demand Diels-Alder (IEDDA) cycloaddition involving 2-pyrones, which display ambiphilic properties due to their unique electronic characteristics. We investigate the mechanisms underlying IEDDA, with a focus on how electron-donating and electron-withdrawing substituents influence reactivity and product selectivity. Various methodologies are reviewed, encompassing non-catalytic and catalytic approaches. Special attention is given to advancements in microwave-assisted techniques and high-pressure conditions, which enhance both reaction efficiency and selectivity. Additionally, the synthesis of chiral bridged bicyclic lactones from substituted 2-pyrones is examined, illustrating their versatility in organic synthesis. This review underscores the significance of IEDDA cycloaddition in pioneering new synthetic routes for building complex molecular structures.

Doping In Vivo Alkylation in E. coli by Introducing the Direct Sulfurylation Pathway of S. cerevisiae

AbstractMethylation and alkylation are important techniques used for the synthesis and derivatisation of small molecules and natural products. Application of S‐adenosylmethionine (SAM)‐dependent methyltransferases (MTs) in biotechnological hosts such as Escherichia coli lowers the environmental impact of alkylation compared to chemical synthesis and facilitates regio‐ and chemoselective alkyl chain transfer. Here, we address the limiting factor for SAM synthesis, methionine supply, to accelerate in vivo methylation activity. Introduction of the direct sulfurylation pathway, consisting of O‐acetylhomoserine sulfhydrolase (ScOAHS) and O‐acetyltransferase (ScMET2), from S. cerevisiae into E. coli and supplementation with methanethiol or the corresponding disulfide improves atom‐economic methylation activity in three different MT reactions. Up to 17‐fold increase of conversion compared to the sole expression of the MT and incorporation of up to 79 % of the thiol compound added were achieved. Promiscuity of ScOAHS allowed in vivo production of methionine analogues from organic thiols. Further co‐overproduction of a methionine adenosyltransferase yielded SAM analogues which were further transferred by MTs onto different substrates. For methylation of non‐physiological substrates, conversion rates up to 73 % were achieved, with an isolated yield of 41 % for N‐methyl‐2,5‐aminonitrophenol. The here described technique enables E. coli to become a biotechnological host for improved methylation and selective alkylation reactions.

Isolated Ni Atoms for Enhanced Photocatalytic H2O2 Performance with 1.05% Solar-to-Chemical Conversion Efficiency in Pure Water.

Photocatalytic hydrogen peroxide (H2O2) production encounters a major impediment in its low solar-to-chemical conversion (SCC) efficiency due to undesired H2O2 product decomposition. Herein, an isolated nickel (Ni) atom modification strategy is developed to adjust the thermodynamic process of H2O2 production to address the challenge. Sacrificial experiments and in situ characterization reveal that H2O2 generation occurs via a highly selective indirect two-electron oxygen reduction reaction. The optimized photocatalyst exhibits a remarkable H2O2 production rate of 338.9 μmol gcat-1 h-1 in pure water, representing a 48-fold enhancement. Notably, it attains an impressive SCC efficiency of 1.05%, surpassing that of current state-of-the-art catalysts. Theoretical insights reveal the downshifted d-band center facilitates moderate O2 adsorption and barrier-free *OOH conversion, favoring H2O2 release and preventing *H2O2 decomposition. This work showcases efficient H2O2 photosynthesis via d-band manipulation, presenting a fresh perspective for advancing high-efficiency SCC systems.

An MEDT Study of the Reaction Mechanism and Selectivity of the Hetero-Diels-Alder Reaction Between 3-Methylene-2,4-Chromandione and Methyl Vinyl Ether.

The hetero-Diels-Alder (HDA) reaction between the ambident heterodiene 3-methylene-2,4-chromandione (MCDO) and non-symmetric methyl vinyl ether (MVE) is investigated using the molecular electron density theory (MEDT) at the B3LYP/6-311G(d,p) computational level. The aim of this study is to gain insight into its molecular mechanism and to elucidate the factors that control the selectivity found experimentally. DFT-based reactivity indices reveal that MCDO exhibits strong electrophilic characteristics, while MVE displays a strong nucleophilic character. Meanwhile, the Parr function explains the ortho regioselectivity of this HDA reaction. The highly polar nature of this HDA reaction, supported by the high global electron density transfer (GEDT) taking place at the transition state structures (TSs), accounts for the very low activation energy associated with the most favorable TS-4on. The ambident nature of MCDO allows for the formation of two constitutional isomeric cycloadducts. In the case of MVE, pseudocyclic selectivity is attained using a thermodynamic control. This polar HDA reaction displays an endo stereoselectivity and a complete ortho regioselectivity. A comparative relative interacting atomic energy (RIAE) analysis of the two diastereomeric structures TS-4on and TS-6on indicates a high degree of likeness, which explains the low pseudocyclic selectivity under kinetic control.

Programmable Plasma-Microdroplet Cascade Reactions for Multicomponent Systems.

The concept of programmable cascade reactions in charged microdroplets is introduced using carbon-carbon (C-C) bond formation via uncatalyzed Michael addition in a three-tier study culminating in programmable Hantzsch multicomponent, multistep reactions. In situ generated reactive oxygen species (ROS) from nonthermal plasma discharge are fused with charged water microdroplets (devoid of ROS) in real time for accelerated chemical reactions. This plasma-microdroplet fusion platform utilizing a coaxial spray configuration enabled product selection while avoiding unwanted side reactions. Hydrogen abstraction via ROS facilitated the formation of enolate anions without strong base use. Reaction enhancement factors >103 were calculated for plasma-microdroplet fusion versus microdroplet-only reactions. The platform programmability was showcased through (i) uncatalyzed 1,4-Michael addition of α,β-unsaturated carbonyls, (ii) novel C-C bond formation via the use of pro-electrophilic amine and alcohol substrates─activated through collisions in the microdroplet environment to serve as Michael acceptors, and (iii) selective Hantzsch cascade reaction with cross-coupling products, avoiding side reactions including N-alkylation and self-coupling product formation. Milligram quantity product collection is achieved, showcasing plasma-microdroplet fusion as an effective tool for preparative-scale synthesis. Thus, the controlled generation of ROS via plasma discharge during charged water microdroplet evolution establishes a green synthetic method for uncatalyzed C-C bond formation.

Taming CO2•- via Synergistic Triple Catalysis in Anti-Markovnikov Hydrocarboxylation of Alkenes.

The direct utilization of carbon dioxide as an ideal one-carbon source in value-added chemical synthesis has garnered significant attention from the standpoint of global sustainability. In this regard, the photo/electrochemical reduction of CO2 into useful fuels and chemical feedstocks could offer a great promise for the transition to a carbon-neutral economy. However, challenges in product selectivity continue to limit the practical application of these systems. A robust and general method for the conversion of CO2 to the polarity-reversed carbon dioxide radical anion, a C1 synthon, is critical for the successful valorization of CO2 to selective carboxylation reactions. We demonstrate herein a hydride and hydrogen atom transfer synergy driven general catalytic platform involving CO2•- for highly selective anti-Markovnikov hydrocarboxylation of alkenes via triple photoredox, hydride, and hydrogen atom transfer catalysis. Mechanistic studies suggest that the synergistic operation of the triple catalytic cycle ensures a low-steady-state concentration of CO2•- in the reaction medium. This method using a renewable light energy source is mild, robust, selective, and capable of accommodating a wide range of activated and unactivated alkenes. The highly selective nature of the transformation has been revealed through the synthesis of hydrocarboxylic acids from the substrates bearing a hydrogen atom available for intramolecular 1,n-HAT process as well as diastereoselective synthesis. This technology represents a general strategy for the merger of in situ formate generation with a synergistic photoredox and HAA catalytic cycle to provide CO2•- for selective chemical transformations.

Atomic‐Level Synergistic Catalysts: Single‐Atom Site Integrated with Atom, Cluster and Nanoparticle

AbstractThe emerging atomic‐level synergistic catalysts based on the single‐atom sites and other valuable components, such as atom, cluster, nanoparticle and other nano‐matter, shine in various catalytic fields. They can integrate the advantages of individual catalytic sites and other valuable components to enhance the activity, selectivity and stability of many chemical reactions via activating their key rate‐determining steps and multistep transformations. In addition, because of the ultrahigh atom utilization (~100 %) and adjustable microenvironment of metal centers, the single‐atom sites can intelligently construct with other useful large size sites to strengthening in tandem a typical catalytic process. Herein, the structure and mechanism of atomic‐level synergistic catalysts with controllable electronic structures and regulatory reaction processes are presented. We particularly emphasize the interactions between active components of atomic‐level synergistic catalysts and catalytic reaction processes, which are essential for understanding how these catalysts are cooperatively working. It is anticipated that this minireview can make the promotion of advanced atomic‐level synergistic catalysts based on single‐atom sites.

Palladium-Catalyzed Ortho Alkoxylation of Oxazoline Derivatives: An Avenue to Reach Meta-Substituted Electron-Rich Arenes Exploiting Oxazoline as a Removeable Directing Group.

An efficient and highly regioselective palladium-catalyzed oxazoline-directed alkoxylation is reported. The reaction proceeds under air and mild temperatures (60 °C). A series of alcohols can be used as alkoxylating agents and concomitantly act as reaction solvents, whereas primary and secondary alcohols are tolerated. Furthermore, fluorinated alcohols can be applied as well, introducing pharmaceutically relevant fluorine-containing groups. 1,3-Dialkoxylated products can be further subjected to hydrolysis transforming the oxazoline-directing group to a carboxylic acid, which can be removed by decarboxylation if desired. This approach demonstrates the capability to reverse the conventional site selectivity of electrophilic aromatic substitution reactions, since it allows the synthesis of arenes with two electron-donating groups in a 1,3-relationship.

Boosting the O2-to-H2O2 Selectivity Using Sn-Doped Carbon Electrocatalysts: Towards Highly Efficient Cathodes for Actual Water Decontamination.

The high cost and often complex synthesis procedure of new highly selective electrocatalysts (particularly those based on noble metals) for H2O2 production are daunting obstacles to penetration of this technology into the wastewater treatment market. In this work, a simple direct thermal method has been employed to synthesize Sn-doped carbon electrocatalysts, which showed an electron transfer number of 2.04 and outstanding two-electron oxygen reduction reaction (ORR) selectivity of up to 98.0 %. Physicochemical characterization revealed that this material contains 1.53 % pyrrolic nitrogen, which is beneficial for the production of H2O2, and -C≡N functional group, which is advantageous for H+ transport. Moreover, the high volume ratio of mesopores to micropores is known to favor the quick escape of H2O2 from the electrode surface, thus minimizing its further oxidation. A purpose-made gas-diffusion electrode (GDE) was prepared, yielding 20.4 mM H2O2 under optimal electrolysis conditions. The drug diphenhydramine was selected for the first time as model organic pollutant to evaluate the performance of an electrochemical advanced oxidation process. In conventional electro-Fenton process (pH 3), complete degradation was achieved in only 15 min at 10 mA cm-2, whereas at natural pH 5.9 and 33.3 mA cm-2, almost overall drug removal was reached in 120 min.

Carbonized Polymer Dots-Promoted Photocatalytic Activation of Molecular Oxygen for Efficient and Selective Oxidation of Thioethers to Sulfoxides.

Sulfoxides are essential in pharmaceuticals and chemicals, yet traditional thioether oxidation struggles with selectivity and sustainability. This study introduces carbonized polymer dots (CPDs) as effective photocatalysts for ecofriendly thioether to sulfoxide oxidation, using water and ethanol to enhance reaction selectivity and efficiency under 455 nm blue light. These catalysts not only show remarkable efficacy under mild conditions but also display high selectivity for sulfoxide formation, proving versatile across a broad range of substrates. We further elucidated the catalytic mechanism, confirming the predominant roles of singlet oxygen and superoxide anions through both spectroscopic evidence and quenching experiments. The method extends to the synthesis of pharmaceuticals such as oxfendazole, albendazole sulfoxide, and sulindac, highlighting its practical utility. Overall, our findings present a sustainable and efficient avenue for sulfoxide synthesis, thereby broadening the practical utility of CPDs in photocatalytic transformations.

Regulating Chlorine and Hydrogen Atom Transfer for Selective Photoelectrochemical C─C Coupling by Cu-coordination Effect at Semiconductor/Electrolyte Interfaces.

Semiconductor-based photoelectrochemical (PEC) organic transformations usually show radical characteristics, in which the reaction selectivity is often difficult to precisely control due to the nonselectivity of radicals. Accordingly, several simple organic reactions (e.g., oxidations of alcohols, aldehydes, and other small molecules) have been widely studied, while more complicated processes like C─C coupling remain challenging. Herein, a synergistic heterogeneous/homogeneous PEC strategy is developed to achieve a controllable radical-induced C─C coupling reaction mediated by the copper-coordination effect at the semiconductor/electrolyte interfaces, which additionally exerts a significant impact on the product regioselectivity. Through experimental studies and theoretical simulations, this study reveals that the copper-chloride complex effectively regulates the formation of chloride radicals, a typical hydrogen atom transfer agent, on semiconductor surfaces and stabilizes the heterogeneous interfaces by suppressing the radical-induced surface passivation. Taking the Minisci reaction (the coupling between 2-phenylquinoline and cyclohexane) as a model, the yield of the target C─C coupling product reaches up to 90% on TiO2 photoanodes with a selectivity of 95% and long-term stability over 100h. Moreover, such a strategy exhibits a broad scope and can be used for the functionalization of various heteroaromatic hydrocarbons.