Dynamic Phase Behavior of Surface-Active Fluorinated Ionic Liquid Epoxidation Catalysts.

We report on the synthesis of amphiphobic fluorinated surface-active ionic liquid (FSAIL) epoxidation catalysts, which show reversible temperature-controlled solubility in water. The solubility of FSAILs containing the catalytically active perrhenate- and tungstate anions was studied in both the aqueous and the substrate phase, showing a significant solubility decrease in both media compared to their non-fluorinated congeners. It was shown that both the epoxide product and the catalyst additive phenylphosphonic acid (PPA) are efficient in transferring the FSAIL catalyst into the organic phase, rendering the reaction homogeneous. The FSAILs were used as catalysts for the epoxidation of olefins using aqueous H2O2 as oxidant, showing an exceptionally high catalytic activity at mild conditions. Catalyst recycling was demonstrated over ten consecutive runs by phase separation and subsequent product distillation.

Spatial-coupled Ampere-level Electrochemical Propylene Epoxidation over RuO2/Ti Hollow-fiber Penetration Electrodes.

The electrochemical propylene epoxidation reaction (PER) provides a promising route for ecofriendly propylene oxide (PO) production, instantly generating active halogen/oxygen species to alleviate chloride contamination inherent in traditional PER. However, the complex processes and unsatisfactory PO yield for current electrochemical PER falls short of meeting industrial application requirements. Herein, a spatial-coupling strategy over RuO2/Ti hollow-fiber penetration electrode (HPE) is adopted to facilitate efficient PO production, significantly improving PER performance to the ampere level (achieving over 80% PO faradaic efficiency and a maximum PO current density of 859 mA cm-2). The synergetic combination of the penetration effect of HPE and the spatial-coupled reaction sequence, enables the realization of ampere-level PO production with high specificity, exhibiting significant potentials for economically viable PER applications.

A Mechanistic Study on Iron-Based Styrene Aziridination: Understanding Epoxidation via Nitrene Hydrolysis.

Transition-metal-catalyzed nitrene transfer reactions are typically performed in organic solvents under inert and anhydrous conditions due to the involved air and water-sensitive nature of reactive intermediates. Overall, this study provides insights into the iron-based ([FeII(PBI)3](CF3SO3)2 (1), where PBI = 2-(2-pyridyl)benzimidazole), catalytic and stoichiometric aziridination of styrenes using PhINTs ([(N-tosylimino)iodo]benzene), highlighting the importance of reaction conditions including the effects of the solvent, co-ligands (para-substituted pyridines), and substrate substituents on the product yields, selectivity, and reaction kinetics. The aziridination reactions with 1/PhINTs showed higher conversion than epoxidation with 1/PhIO (iodosobenzene). However, the reaction with PhINTs was less selective and yielded more products, including styrene oxide, benzaldehyde, and 2-phenyl-1-tosylaziridine. Therefore, the main aim of this study was to investigate the potential role of water in the formation of oxygen-containing by-products during radical-type nitrene transfer catalysis. During the catalytic tests, a lower yield was obtained in a protic solvent (trifluoroethanol) than in acetonitrile. In the case of the catalytic oxidation of para-substituted styrenes containing electron-donating groups, higher yield, TON, and TOF were achieved than those with electron-withdrawing groups. Pseudo-first-order kinetics were observed for the stoichiometric oxidation, and the second-order rate constants (k2 = 7.16 × 10-3 M-1 s-1 in MeCN, 2.58 × 10-3 M-1 s-1 in CF3CH2OH) of the reaction were determined. The linear free energy relationships between the relative reaction rates (logkrel) and the total substituent effect (TE, 4R-PhCHCH2) parameters with slopes of 1.48 (MeCN) and 1.89 (CF3CH2OH) suggest that the stoichiometric aziridination of styrenes can be described through the formation of a radical intermediate in the rate-determining step. Styrene oxide formation during aqueous styrene aziridination most likely results from oxygen atom transfer via in situ iron oxo/oxyl radical complexes, which are formed through the hydrolysis of [FeIII(N•Ts)] under experimental conditions.

An Integrated Module Performs Selective 'On-Line' Epoxidation in the Biosynthesis of the Antibiotic Mupirocin.

The delineation of the complex biosynthesis of the potent antibiotic mupirocin, which consists of a mixture of pseudomonic acids (PAs) isolated from Pseudomonas fluorescens NCIMB 10586, presents significant challenges and the timing and mechanisms of several key transformations remain elusive.   Particularly intriguing are the steps that process the linear backbone from the initial polyketide assembly phase to generate the first cyclic intermediate PA-B. These include epoxidation as well as incorporation of the tetrahydropyran (THP) ring and fatty acid sidechain required for biological activity. Here, we show that the mini-module MmpE performs a rare online (ACP-substrate) epoxidation and is integrated ('in-cis') into the polyketide synthase via a docking domain. A linear polyketide fragment with 6 asymmetric centres was synthesised using a convergent approach and used to demonstrate substrate flux via an atypical KS0 and a previously unannotated ACP (MmpE_ACP). MmpE_ACP-bound synthetic substrates were critical in demonstrating successful epoxidation in vitro by the purified MmpE oxidoreductase domain. Alongside feeding studies, these results confirm the timing as well as chain length dependence of this selective epoxidation. These mechanistic studies pinpoint the location and nature of the polyketide substrate prior to the key formation of the THP ring and esterification that generate PA-B.

Magnetic whole-cell biocatalyst based on intracellular lipases of Candida catenulata as promising technology for green synthesis of epoxy fatty acids.

This study focuses on the development a green synthesis of epoxy fatty acids (EFAs) which are commonly used as the plasticizer in polymer industries. The intracellular lipases of Candida catenulata cells as a whole-cell biocatalyst (WCB) were examined in the bio-epoxidation of free fatty acids (FFAs) with hydrogen peroxide. The FFAs in soybean soap stock, an industrial by-product of vegetable oil factories, was used as the feedstock of the process. To remove phosphates from soap stock a degumming process was tested before the bio-epoxidation reaction and results revealed that the EFAs yield was improved using the degummed fatty acids (DFAs). The attachments of magnetic Fe3O4 nanoparticles to the surface of WCBs facilitated the recovery of the biocatalyst, and were improved stabilities. The activation energy for the magnetic whole-cell biocatalysts (MWCB) was 48.54 kJ mol-1, which was lower than the WCB system (51.28 kJ mol-1). The EFA yield was about 47.1 % and 33.8 % after 3 h for the MWCBs and 2 h for the WCBs, respectively. The MWCBs displayed acceptable reusability in the repetitious bio-epoxidation reaction with maintaining 59 % of the original activity after 5 cycles whereas the performance of the WCBs was 5.9 % at the same conditions. The effects of influential factors such as reaction time, molar ratio of H2O2 to CC, and batch and semi-batch operations were investigated for both biocatalyst systems. The quality of EFAs was characterized by FTIR and GC-MS analyses.

Impacting the Surface Chemistry of NiAu by Immobilizing on MgO/N-rich Nanoporous Carbon Heterostructures for Boosting Catalytic Activities.

Tuning the physical and chemical interaction between metal-metal' (M-M') and metal-support is an ideal way to realize enhanced catalytic activity of metal nanoparticles (NPs). As a proof of concept, herein we report the fabrication of nickel-gold (Ni-Au) alloy nanoparticles attached to N-doped nanoporous carbon (NPC) intervened with MgO (Ni73Au27@MgO-NPC), achieved through the impregnation of metal precursors into Schiff-base network polymer (SNP) framework along with Mg(OH)2 and pyrolysis at 800 °C in N2 atmosphere. With high stability and heterogeneity, the nickel rich Ni73Au27@MgO-NPC exhibited higher catalytic activities with turnover frequencies of 29,272 h-1 (hydrogenation of p-nitrophenol), 93,843 h-1 (degradation of methyl orange), and 2,218 h-1 (epoxidation of stilbene). Enhanced catalytic activity is correlated to the synchronized electron density enhancement in Au, by Ni and MgO/N-rich nanoporous carbon heterostructures, as evident from detailed X-ray photoelectron spectroscopic studies.

Rational design of isolated tetrahedrally coordinated Ti(IV) sites in zeolite frameworks for methyl oleate epoxidation.

The rational design of isolated metals containing zeolites is crucial for the catalytic conversion of biomass-derived compounds. Herein, we explored the insertion behavior of the isomorphic substitution of Ti(IV) in different zeolite frameworks, including ZSM-35 (FER), ZSM-5, and BEA. The different aluminium topological densities of each zeolite framework lead to the creation of different degrees of vacant sites for hosting the tetrahedrally coordinated Ti(IV) active sites. These observations show the precise control of the degree of four-coordinated Ti(IV) sites in a zeolite framework, especially in BEA topology, by tuning the degree of unoccupied sites in the host zeolite structure via dealumination. Interestingly, the more vacancies in the host zeolite structure, the more isolated tetrahedrally coordinated Ti(IV) can be increased, eventually enhancing the catalytic performance in methyl oleate (MO) epoxidation for producing methyl-9,10-epoxystearate (EP). The engineered Ti-ß exhibits outstanding performances in bulky MO epoxidation with the amount of produced EP per number of Ti sites up to 17.1 ± 1.8 mol mol-1. This observation discloses an alternative strategy for optimizing catalyst efficiency in the rational design of the Ti-embedding zeolite catalyst, endeavoring to reach highly efficient catalytic performance.

Transition Metal-Catalyzed Transformations of Chalcones.

Chalcones are a class of naturally occurring flavonoid compounds associated to a variety of biological and pharmacological properties. Several reviews have been published describing the synthesis and biological properties of a vast array of analogues. However, overviews on the reactivity of chalcones has only been explored in a few accounts. To fill this gap, a systematic survey on the most recent developments in the transition metal-catalyzed transformation of chalcones was performed. The chemistry of copper, palladium, zinc, iron, manganese, nickel, ruthenium, cobalt, rhodium, iridium, silver, indium, gold, titanium, platinum, among others, as versatile catalysts will be highlighted, covering the literature from year 2000 to 2023, in more than 380 publications.

Oxidovanadium(V) Schiff Base Complexes Derived from Chiral 3-amino-1,2-propanediol Enantiomers: Synthesis, Spectroscopic Studies, Catalytic and Biological Activity.

Oxidovanadium(V) complexes, [(+)VOL1-5] and [(-)VOL1-5], with chiral tetradentate Schiff bases, which are products of monocondensation of S(‒)-3-amino-1,2-propanediol or R(+)-3-amino-1,2-propanediol with salicylaldehyde derivatives, have been synthesized. Different spectroscopic methods, viz. 1H and 51V NMR, IR, UV-Vis, and circular dichroism, as well as elemental analysis, have been used for their detailed characterization. Furthermore, the epoxidation of styrene, cyclohexene, and two monoterpenes, S(‒)-limonene and (‒)-α-pinene, using two oxidants, aqueous 30% H2O2 or tert-butyl hydroperoxide (TBHP) in decane, has been studied with catalytic amounts of all complexes. Finally, biological cytotoxicity studies have also been performed with these oxidovanadium(V) compounds for comparison with cis-dioxidomolybdenum(VI) Schiff base complexes with the same chiral ligands, as well as to determine the cytoprotection against the oxidative damage caused by 30% H2O2 in the HT-22 hippocampal neuronal cells in the range of their 10-100 µM concentration.

Molecular Basis for Chemoselectivity Control in Oxidations of Internal Aryl-Alkenes Catalyzed by Laboratory Evolved P450s.

P450 enzymes naturally perform selective hydroxylations and epoxidations of unfunctionalized hydrocarbon substrates, among other reactions. The adaptation of P450 enzymes to a particular oxidative reaction involving alkenes is of great interest for the design of new synthetically useful biocatalysts. However, the mechanism that these enzymes utilize to precisely modulate the chemoselectivity and distinguishing between competing alkene double bond epoxidations and allylic C-H hydroxylations is sometimes not clear, which hampers the rational design of specific biocatalysts. In a previous work, a P450 from Labrenzia aggregata (P450LA1) was engineered in the laboratory using directed evolution to catalyze the direct oxidation of trans-ß-methylstyrene to phenylacetone. The final variant, KS, was able to overcome the intrinsic preference for alkene epoxidation to directly generate a ketone product via the formation of a highly reactive carbocation intermediate. Here, additional library screening along this evolutionary lineage permitted to serendipitously detect a mutation that overcomes epoxidation and carbonyl formation by exhibiting a large selectivity of 94 % towards allylic C-H hydroxylation. A multiscalar computational methodology was applied to reveal the molecular basis towards this hydroxylation preference. Enzyme modelling suggests that introduction of a bulky substitution dramatically changes the accessible conformations of the substrate in the active site, thus modifying the enzymatic selectivity towards terminal hydroxylation and avoiding the competing epoxidation pathway, which is sterically hindered.

Stereoconvergent Approach to the Enantioselective Construction of α-Quaternary Alcohols by Radical Epoxide Allylation.

We describe a highly stereoconvergent radical epoxide allylation towards diastereomerically and enantiomerically enriched α-quaternary alcohols in two steps from olefins. Our approach combines the stereospecifity and enantioselectivity of the Shi epoxidation with the unprecedented Ti(III)-promoted intramolecular radical group transfer allylation of epoxides. A directional isomerization step via configurationally labile radical intermediates enables the selective preparation of all-carbon quaternary stereocenters in a unique fashion.

Boosting the Faradaic Efficiency of Br--Mediated Photoelectrochemical Epoxidation by Local Acidity on α-Fe2O3.

The redox mediated photoelectrochemical (PEC) or electrochemical (EC) alkene oxidation process is a promising method to produce high value-added epoxides. However, due to the competitive reaction of water oxidation and overoxidation of the mediator, the utilization of the electricity is far below the ideal value, where the loss of epoxidation's faradaic efficiency (FE) is ≈50%. In this study, a Br-/HOBr-mediated method is developed to achieve a near-quantitative selectivity and ≈100% FE of styrene oxide on α-Fe2O3, in which low concentration of Br- as mediator and locally generated acidic micro-environment work together to produce the higher active HOBr species. A variety of styrene derivatives are investigated with satisfied epoxidation performance. Based on the analysis of local pH-dependent epoxidation FE and products distribution, the study further verified that HOBr serves as the true active mediator to generate the bromohydrin intermediate. It is believed that this strategy can greatly overcome the limitation of epoxidation FE to enable future industrial applications.

A Safe One-Pot Synthesis and Characterization of Epoxidized Moringa Oleifera Oil.

Global demand for epoxidized vegetable oil has been steadily growing. Epoxidized vegetable oils are typically produced using a two-pot synthesis process in which the oxidation and epoxidation reactions are carried out sequentially. This two-pot synthesis method, however, has a major drawback in industrialscale production, particularly when it comes to operational and process safety issues. A laboratory-scale one-pot synthesis method was attempted in this study with the aim to safely synthesize epoxidized Moringa Oleifera oil (eMOo) by avoiding the occurrence of undesired exothermic runaway reaction. The oil extracted from Moringa Oleifera oil seed kernel (MOo) was used as a starting component due to its high degree of unsaturation and also because the Moringa Oleifera plant can be freely grown in any soil conditions. Two parallel oxidation and epoxidation reactions were carried out simultaneously in this one-pot synthesis method to produce eMOo. The effect of five different mole ratios of MOo, acetic acid and hydrogen peroxide (1:1:1, 1:1:2, 1:1.5:2, 1:1.75:2 and 1:2:2, respectively) on reaction mechanism was investigated at the controlled temperature range of 43 - 55°C and reaction time of 0 - 120 min. The physicochemical properties of MOo as well as the oxirane oxygen content (OOC) of the resulting eMOo were characterized. In addition, GC-MS and FTIR analysis were performed to verify the molecular composition of MOo and also to identify the epoxy group of the resulting eMOo respectively. Among the five different mole ratios studied, the 1:1.5:2 mole ratio has the highest unsaturation conversion of 79.57% and OOC of 4.12%.

A tale of two topological isomers: Uptuning [FeIV(O)(Me4cyclam)]2+ for olefin epoxidation.

TMC-anti and TMC-syn, the two topological isomers of [FeIV(O)(TMC)(CH3CN)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, or Me4cyclam), differ in the orientations of their FeIV=O units relative to the four methyl groups of the TMC ligand framework. The FeIV=O unit of TMC-anti points away from the four methyl groups, while that of TMC-syn is surrounded by the methyl groups, resulting in differences in their oxidative reactivities. TMC-syn reacts with HAT (hydrogen atom transfer) substrates at 1.3- to 3-fold faster rates than TMC-anti, but the reactivity difference increases dramatically in oxygen-atom transfer reactions. R2S substrates are oxidized into R2S=O products at rates 2-to-3 orders of magnitude faster by TMC-syn than TMC-anti. Even more remarkably, TMC-syn epoxidizes all the olefin substrates in this study, while TMC-anti reacts only with cis-cyclooctene but at a 100-fold slower rate. Comprehensive quantum chemical calculations have uncovered the key factors governing such reactivity differences found between these two topological isomers.

High-electrophilic (SiO)2Nb(OH)(=O) sites confined in silanol defects over Nb-Beta zeolite for efficient cyclic alkene epoxidation reactions.

Dealuminated Beta zeolite has a large amount of silanol defects on its interface, which provides an ideal place for embedding metal species and creating metal active sites in a confined microenvironment. The confined metal sites as well as their surroundings are closely related to the reactant activation and transient state achievement. Hence, unraveling the confined metal sites is of great significance for the catalytic reaction process. Herein, niobium species were incorporated into the silanol defects over dealuminated Beta zeolite with a facile dry impregnation method, co-grinding the niobium precursor with dealuminated Beta zeolite support. The successful incorporation of niobium into the silanol defects for 30Nb-Beta zeolite was verified by DRIFT, 1H MAS NMR, UV-Vis and UV-Raman characterizations. XAS characterization and DFT calculations further disclosed that the confined Nb species existed as (SiO)2Nb(OH)(=O), containing two Si-O-Nb bonds, one Nb=O bond as well as one Nb-OH bond. The synthesized 30Nb-Beta zeolite catalyst displayed a superior cyclohexene conversion of 51.1%, cyclohexene oxide selectivity of 83.1% as well as TOF value of 188.2 h-1 ascribed to the inherent electrophilicity of Nb(V) for confined (SiO)2Nb(OH)(=O) species as well as the low oxygen transfer energy barrier for NbV-OOH species. Furthermore, the prepared 30Nb-Beta zeolite can be effectively employed to other cyclic alkene epoxidation reactions.

In Situ Observation of Solvent-Mediated Cyclic Intermediates during the Alkene Epoxidation/Hydration over a Ti-Beta/H2O2 System.

Solvent effects in catalytic reactions have received widespread attention as they can promote reaction rates and product selectivities by orders of magnitude. It is well accepted that the stable five-membered cyclic intermediates formed between the solvent molecules and Ti species are crucial to the alkene epoxidation in a heterogeneous Ti(IV)-H2O2 system. However, the direct spectroscopic evidence of these intermediates is still missing and the corresponding reaction pathway for the alkene epoxidation remains unclear. By combining in situ 13C MAS NMR, two-dimensional (2D) 1H-13C heteronuclear correlation (HETCOR) NMR spectroscopy and theoretical calculations, the five-membered ring structures, where the protic solvents (ROH), and aprotic solvent (acetone), coordinate and stabilize the active Ti species, are identified for the first time over Ti-Beta/H2O2 system. Moreover, the role of these cyclic intermediates in the alkene epoxidation/hydration conversion is clarified. These results provide new insights into the solvent effect in liquid-phase epoxidation/hydration reactions over Ti(IV)-H2O2 system.

Boosting Electrocatalytic Ethylene Epoxidation by Single Atom Modulation.

The electrochemical synthesis of ethylene oxide (EO) using ethylene and water under ambient conditions presents a low-carbon alternative to existing industrial production process. Yet, the electrocatalytic ethylene epoxidation route is currently hindered by largely insufficient activity, EO selectivity, and long-term stability. Here we report a single atom Ru-doped hollandite structure KIr4O8 (KIrRuO) nanowire catalyst for efficient EO production via a chloride-mediated ethylene epoxidation process. The KIrRuO catalyst exhibits an EO partial current density up to 0.7 A cm-2 and an EO yield as high as 92.0 %. The impressive electrocatalytic performance towards ethylene epoxidation is ascribed to the modulation of electronic structures of adjacent Ir sites by single Ru atoms, which stabilizes the *CH2CH2OH intermediate and facilitates the formation of active Cl2 species during the generation of 2-chloroethanol, the precursor of EO. This work provides a single atom modulation strategy for improving the reactivity of adjacent metal sites in heterogeneous electrocatalysts.

CO2-Free Ethylene Oxide Production via Liquid-Phase Epoxidation with Fe2O3/MSM Catalyst.

In this study, we present an approach for ethylene oxide (EO) production that addresses environmental concerns by eliminating greenhouse gas emissions. Our catalyst, Fe2O3/MSM, was synthesized using a hydrothermal method, incorporating Fe2O3 nanoparticles into a well-structured mesoporous silica matrix (MSM). We selected peracetic acid as the oxidant, enabling CO2-free EO production while yielding valuable by-products such as acetic acid, monoethylene glycol, and diethylene glycol. X-ray diffraction (XRD), X- ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) analyses confirmed the heteroatom structure of the catalysts and porosity, while Transmission electron microscopy (TEM) analysis provided insights into its morphology. Then, the synthesized catalyst was used in the liquid-phase epoxidation of ethylene for EO production. Our systematic experiments involved varying critical parameters such as temperature, ethylene to oxidant ratio, catalyst dosage, and solvent to optimize EO selectivity and ethylene conversion. The results of this study demonstrated an 80.2 % ethylene conversion to EO with an EO selectivity of 87.6 %. The production process yielded valuable by-products without CO2 emissions, highlighting its environmental friendliness.

Practical Epoxidation of Olefins Using Air and Ubiquitous Iron-Based Fluorous Salen Complex.

The epoxidation of olefins by substituting "air" for potentially harmful oxidants was achieved using an oxidation method that integrated a fluorous iron(III) salen catalyst derived from common metals and pivalaldehyde. Several aromatic disubstituted olefins were converted into their corresponding epoxides with high efficiency and quantitative yields. This reaction represents an environmentally friendly oxidation process that utilizes an abundant source of air and employs a readily available metal, iron, in the form of salen complexes, making it an environmentally conscious oxidation reaction.

Preparative and Catalytic Properties of MoVI Mononuclear and Metallosupramolecular Coordination Assemblies Bearing Hydrazonato Ligands.

A series of polynuclear, dinuclear, and mononuclear Mo(VI) complexes were synthesized with the hydrazonato ligands derived from 5-methoxysalicylaldehyde and the corresponding hydrazides (isonicotinic hydrazide (H2L1), nicotinic hydrazide (H2L2), 2-aminobenzhydrazide (H2L3), or 4-aminobenzhydrazide (H2L4)). The metallosupramolecular compounds obtained from non-coordinating solvents, [MoO2(L1,2)]n (1 and 2) and [MoO2(L3,4)]2 (3 and 4), formed infinite structures and metallacycles, respectively. By blocking two coordination sites with cis-dioxo ligands, the molybdenum centers have three coordination sites occupied by the ONO donor atoms from the rigid hydrazone ligands and one by the N atom of pyridyl or amine-functionalized ligand subcomponents from the neighboring Mo building units. The reaction in methanol afforded the mononuclear analogs [MoO2(L1-4)(MeOH)] (1a-4a) with additional monodentate MeOH ligands. All isolated complexes were tested as catalysts for cyclooctene epoxidation using tert-butyl hydroperoxide (TBHP) as an oxidant in water. The impact of the structure and ligand lability on the catalytic efficiency in homogeneous cyclooctene epoxidation was elucidated based on theoretical considerations. Thus, dinuclear assemblies exhibited better catalytic activity than mononuclear or polynuclear complexes.