Reaction Steps Research Articles

Theoretical calculations and experimental verification of carbon dioxide reduction electrocatalyzed by metalloporphyrin

Metal-functionalized porphyrin-like graphene structures are promising electrocatalysts for carbon dioxide reduction reaction (CO2RR) as their metal centers can modulate activity. Yet, the role of metal center of metalloporphyrins (MTPPs) in CO2 reaction activity is still lacking deep understanding. Here, CO2RR mechanism on MTPPs with five different metal centers (M = Fe, Co, Cu, Zn and Ni) are examined by first-principles calculations. The *COOH formation is the rate determined step on the five MTPP structures, and the CoTPP exhibits the best CO2RR activity while ZnTPP and NiTPP are the worst, which is also verified by our experiment. The CO2RR activity is controlled by adsorption states of intermediates (*CO, *COOH), i.e., chemisorption (e.g., on CoTPP) and physisorption (on ZnTPP and NiTPP) of intermediates will lead to good and poor activity, respectively. The deeper the d-band center of the porphyrin ring complexed metal atom, the weaker bonding of MTPP with CO and COOH. Theoretical calculations and experimental results indicate that MTPPs with Co and Fe centers lead to a reduction in the energy barriers for the two uphill reaction steps in the electrocatalytic CO2 reduction process, thereby enhancing CO2 reduction electrocatalytic activity. Faradaic efficiency of CO is correlated with the reaction energy barrier of the first proton-coupled electron reduction process, displaying a strong linear correlation. This work provides a fundamental understanding of MTPPs used as electrocatalysts for CO2RR.

One‐Pot Three‐Component Synthesis of Biologically Promising Indenoquinoxaline Fused Spiroheterocycles Starting from 11H‐indeno[1,2‐b]quinoxalin‐11‐ones

AbstractHeterocycles are very common in many naturally occurring bioactive compounds as well as in the commercially available drug molecules. Very recently spiroheterocycles have gained considerable attention due to their wide range of pharmacological applicability. Among many others, 11H‐indeno[1,2‐b]quinoxalin‐11‐one in recent time have gained significant attention as an important building block to prepare structurally diverse biologically promising spiroheterocycles under various reaction conditions. On the other hand, it was found that one‐pot three‐component reaction strategy plays an important role in the preparation of spiroheterocycles starting from 11H‐indeno[1,2‐b]quinoxalin‐11‐one as it has many advantages including high atom economy, operational simplicity, easy workup procedures, reduction of byproducts, energy and reaction step efficiency etc. In this review, we have discussed all the recent developments related to the one‐pot three‐component synthesis of biologically promising indenoquinoxaline fused spiroheterocycles starting from 11H‐indeno[1,2‐b]quinoxalin‐11‐ones under diverse reaction conditions.

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes.

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO2, H2O, and O2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. The emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

Activating Nitrogen for Electrochemical Ammonia Synthesis via an Electrified Transition-Metal Dichalcogenide Catalyst.

The complex interplay between local chemistry, the solvent microenvironment, and electrified interfaces frequently present in electrocatalytic reactions has motivated the development of quantum chemical methods that can accurately model these effects. Here, we predict the thermodynamics of the nitrogen reduction reaction (NRR) at sulfur vacancies in 1T'-phase MoS2 and highlight how the realistic treatment of potential within grand canonical density functional theory (GC-DFT) seamlessly captures the multiple competing effects of applied potential on a catalyst interface interacting with solvated molecules. In the canonical approach, the computational hydrogen electrode is widely used and predicts that adsorbed N2 structure properties are potential-independent. In contrast, GC-DFT calculations show that reductive potentials activate N2 toward electroreduction by controlling its back-bonding strength and lengthening the N-N triple bond while decreasing its bond order. Similar trends are observed for another classic back-bonding ligand in CO, suggesting that this mechanism may be broadly relevant to other electrochemistries involving back-bonded adsorbates. Furthermore, reductive potentials are required to make the subsequent N2 hydrogenation steps favorable but simultaneously destabilizes the N2 adsorbed structure resulting in a trade-off between the favorability of N2 adsorption and the subsequent reaction steps. We show that GC-DFT facilitates modeling all these phenomena and that together they can have important implications in predicting electrocatalyst selectivity for the NRR and potentially other reactions.

Process intensification for production of dispersants via integration of reaction and separation in a horizontal thin film evaporator

Process intensification can be achieved in specialty chemicals manufacturing via transition from batch-to-continuous processing. However, the absence of headspace in a continuous tubular reactor limits the ability to remove volatile byproducts from the reacting liquid flow. Previous studies showed that the production of succinimide dispersants follows a two-step amidation-dehydration pathway in which water is formed as a by-product. The inability to remove this water imposed a thermodynamic equilibrium limitation on the dehydration step, and hence necessitated a downstream drying step to obtain a dehydrated dispersant product within commercial specifications. In the present study, the use of an agitated, horizontal thin film evaporator (TFE) was investigated as a continuously operated reactive separator which combines reaction and dehydration into a single operating unit, reducing the overall cost and physical footprint of the process. The continuous TFE unit was first experimentally investigated as a stand-alone, integrated reactor-separator. Using this configuration, the obtained imide yield consistently exceeded the maximum thermodynamic yield at each operating temperature, confirming the efficiency of the integrated reaction and separation steps in the TFE. Next, the unit was modeled by integrating reaction kinetics with mass and energy balance equations, using appropriate correlations for heat and mass transfer from the literature which were verified for the experimental set-up. This model provided insights into the system behavior across different operating conditions, including the role of forward and reverse reactions along the TFE unit length. The model was then used to confirm the feasibility of replacing the two-step tubular reactor-evaporator process with a single TFE unit as an intensified reactive separator, further reducing the physical footprint of the process by enabling compact modular process designs.

Efficient electrocatalytic formate oxidation on copper oxide catalyst mediated lithium recovery coupled hydrogen production

In response to the increase in retired lithium-ion batteries (LIBs), there is a rising trend in lithium recycling, which can not only address the scarcity of lithium resources but also mitigate environmental pollution caused by battery waste. In this study, we present an electrocatalytic strategy for formate oxidation reaction (FOR) aimed at facilitating lithium recovery coupled hydrogen production. The obtained results have indicated that the synthesized Cu-based oxide can efficiently catalyze FOR, achieving a current density of 500 mA cm−2 at only 1.534 V vs. RHE. According to density functional theory calculations, the adsorption strength of the intermediate specie HCOO on Cu-based oxide is reduced (−0.36 eV) compared to Ni-based oxide (−2.27 eV), resulting in a thermodynamically favorable step for the rate-determining HCOO dehydrogenation reaction. Assembling a FOR coupled hydrogen evolution reaction (HER) electrolysis system can achieve hydrogen production and Li recovery (Li recovery product is Li2CO3) by electrolyzing alkaline raffinate containing lithium. This approach eliminates the need for additional formic acid and sodium carbonate, thereby reducing material consumption and ultimately enhancing the economic efficiency of the lithium battery recovery strategy.

Modulation of energy barrier of reaction steps over S-doped Ni(OH)2/Cu composites to achieve high-performance urea electrolysis catalysts

Ni(OH)2 has been found a cost-effective and promising electrocatalyst for urea oxidation reaction (UOR). However, HER activity is challenging due to its weak adsorption of active H atoms, poor water dissociation, and low conductivity. In this study, heteroatomic S-doped Ni(OH)2/Cu composite has been synthesized using the one-pot electrodeposition process. The incorporation of S atoms significantly enhanced the electron transfer rate and adsorption of active H atoms, which promoted the UOR and HER process. Similarly, the metallic Cu with S-doped Ni(OH)2 also exhibited the synergistic effect and promoted water dissociation, adsorption of active H atoms. As expected, S-doped Ni(OH)2/Cu composites exhibit remarkable urea electrolysis activity with a small cell voltage of 1.35 V to approach the current density of 10 mA cm−2. Results indicate that the adopted strategy has been found effective and the prepared composite is a good bifunctional urea electrolysis catalyst.

Synthesis and photoinitiated cationic polymerization of epoxy monomers derived from oleic acid comprising one to three epoxy groups

A series of bio-based epoxy compounds based on oleic acid combined with aliphatic or aromatic structures were studied regarding selected properties such as melting behavior and viscosity as well as their reactivity in a photoinitiated cationic polymerization. The new epoxy compounds derived from oleic acid and either eugenol or isoeugenol, epoxidized triolein, and an epoxy compound derived from oleic acid and popane diol-1,3 contain 100 % renewable carbon. Atom economy differs not only for the esterification and epoxidation reaction, also selection of hydrogen peroxide or m-chloroperbenzoic acid for the epoxidation significantly influences the atom economy of this reaction step. Variation of the chemical structure of the bio-based epoxy compounds derived from oleic acid and either an aliphatic alcohol or a phenolic compound results in differences in both melting behavior and viscosity of the epoxy monomers that is important for the photoinitiated cationic polymerization. Kinetic investigation of the photoinitiated cationic polymerization of the bio-based epoxy compounds using photo-DSC shows significant differences in the polymerization rate and conversion as a function of the irradiation time for the epoxy monomers. RT-FTIR spectroscopy gives additional information about the polymerization kinetics for epoxy monomers that are liquid at room temperature. The glass transition temperature of the photopolymers analyzed by DSC is mostly below room temperature that is attributed to the high content of flexible structures containing in the polymers. Additional investigation of the soluble photopolymers by GPC resulted in a molecular weight corresponding to the oligomer region and a dispersity higher than one. The bio-based epoxy monomers comprising two or three epoxy groups may be interesting for application, e. g. in coatings or adhesives, because photoinitiated polymerization results in crosslinking. Epoxy compounds containing only one epoxy group may be useful for viscosity reduction of the photopolymerizing mixtures because of their lower viscosity compared to the epoxy monomers comprising more than one epoxy group.

Dynamic role of dopant and graphene on BiVO4 photoanode for enhanced photoelectrochemical hydrogen production

The development of an efficient and stable electrode remains an attractive challenge for photoelectrochemical (PEC) water splitting to generate cheaper and green hydrogen (H2). Herein, we have fabricated a novel multicomponent molybdenum (Mo) doped bismuth vanadate/graphene (Mo-doped BiVO4@graphene) photoanode by simple spin coating technique followed by an annealing process. Precise control over Mo and graphene doping concentration (GR3/BVO:Mo-0.5) was attained, enabling excellent photocurrent density (4-fold increase as compared to BVO) with an enhanced rate of H2 production. This is attributed to the synergistic effect between molybdenum and graphene enhancing charge carrier density and suppressing the recombination rate of photo-generated electrons and holes. Our DFT studies indicate a reduction in the band gap value after doping pure BVO with Mo. In addition, we observed that the potential determining step of the oxygen evolution reaction (OER) is the electrochemical adsorption of hydroxyl radical (H2O(l) + * → HO* + H+(aq) + e−), which is reduced by ∼0.8 eV after doping with Mo. This study reports on the unique design of a Mo-doped BiVO4@graphene hybrid electrode, which can be used as a superior electrode for green hydrogen generation under sunlight.

Comparing mass transfer and reaction rate kinetics in starch hydrolysis during food digestion

AbstractThis study demonstrates evidence that the mass transfer process of an enzyme (a biocatalyst) is the rate‐limiting step in the starch hydrolysis reaction during food digestion. The significance of this work has been to compare the reaction rate of starch hydrolysis by salivary enzymes with the mass transfer rate of rate‐limiting enzymes. This research has applied mass transfer and reaction engineering theory in a quantitative study of starch hydrolysis, and a dimensionless group, the Damköhler number (Da), has been calculated based on glucose measurements from a beaker and stirrer system. The values of the Da number in this study (0.3–19) indicate that both the time constant for mass transfer and the time constant for reaction are significant parameters. Scanning electron microscopy images emphasize that compression (simulated mastication) helps to break the plant cell wall of starch. Mass‐transfer resistance needs to be considered during food digestion studies. The Da numbers are significantly affected by both compression forces (internal mass‐transfer coefficients) and stirrer speeds (external mass‐transfer coefficients) in this beaker and stirrer system.

Parametric Analysis of Donor Activation for Glycosylation Reactions.

The chemical synthesis of complex oligosaccharides relies on efficient and highly reproducible glycosylation reactions. The outcome of a glycosylation is contingent upon several environmental factors, such as temperature, acidity, the presence of residual moisture, as well as the steric, electronic, and conformational aspects of the reactants. Each glycosylation proceeds rapidly and with a high yield within a rather narrow temperature range. For better control over glycosylations and to ensure fast and reliable reactions, a systematic analysis of 18 glycosyl donors revealed the effect of reagent concentration, water content, protecting groups, and structure of the glycosyl donors on the activation temperature. With these insights, we parametrize the first step of the glycosylation reaction to be executed reliably and efficiently.

Bimetal organic framework derived CoM@N–C composites as bifunctional oxygen catalysts for Zn-air batteries

Metal-loaded nitrogen-doped carbon (M@N–C) catalysts have shown promise as electrocatalysts for replacing noble metal catalysts in industrial processes. To study the influence on structural and performance caused by different bimetal doping, a family of bimetals CoM@N–C (M = Cu/Ni/Fe) composites with porous surface and abundant C defects were well-designed. After bimetallic doping, more defects are introduced into the carbon frameworks, and the metal-N species are fixed. As such, efficient utilization of active sites and rapid mass transfer make the reaction kinetics process more favorable and stable. Density functional theory calculations indicate that Cu/Ni doping optimizes the electronic environment of the Co–N, resulting in the balanced adsorption and dissociation of oxygen intermediates. While the synergy of FeCo activates the O=O, which promotes the sharp decrease in free energy of ∗OOH to ∗O, shifting the rate-determining step for oxygen reduction reaction. This indicates the adsorption site transfer of CoFe0.05@N–C in oxygen reduction and evolution reactions. The CoFe0.05@N–C catalyst exhibits superior bifunctional catalytic activity (with a potential gap of 0.80 V) than that of Pt catalysts. This work presents a simple strategy to fabricate well-defined bimetals doping in bifunctional oxygen electrocatalysts and it is expected to inspire future work on the role of electronic structure modulation and interface engineering.

Selective Hydrofunctionalization of Alkenyl Fluorides Enabled by Nickel-Catalyzed Hydrogen Atoms and Group Transfer: Reaction Development and Mechanistic Study.

Due to the unique effect of fluorine atoms, the efficient construction of high-value alkyl fluorides has attracted significant interest in modern drug development. However, enantioselective catalytic strategies for the efficient assembly of highly functionalized chiral C(sp3)-F scaffolds from simple starting materials have been underutilized. Herein, we demonstrate a nickel-catalyzed radical transfer strategy for the efficient, modular, asymmetric hydrogenation and hydroalkylation of alkenyl fluorides with primary, secondary, and tertiary alkyl halides under mild conditions. The transformation provides facile access to various structurally complex secondary and tertiary α-fluoro amide products from readily available starting materials with excellent substrate compatibility and distinct selectivity. Furthermore, the utility of this method is demonstrated by late-stage modifications and product derivatizations. Detailed mechanistic studies and DFT calculations have been conducted, showing that the rate-determining step for asymmetric hydrogenation reaction is NiH-HAT toward alkenyl fluorides and the stereo-determining step is alcohol coordination to Ni-enolates followed by a barrierless protonation. The mechanism for the asymmetric hydroalkylation reaction is also delivered in this investigation.

Rationally designing of Co-WS2 catalysts with optimized electronic structure to enhance hydrogen evolution reaction

Designing and developing cost-effective, high-performance catalysts for hydrogen evolution reaction (HER) is crucial for advancing hydrogen production technology. Tungsten-based sulfides (WSx) exhibit great potential as efficient HER catalysts, however, the activity is limited by the larger energy required for water dissociation under alkaline conditions. Herein, we adopt a top-down strategy to construct heterostructure Co-WS2 nanofiber catalysts. The experimental results and theoretical simulations unveil that the work functions-induced built-in electric field at the interface of Co-WS2 catalysts facilitates the electron transfer from Co to WS2, significantly reducing water dissociation energy and optimizing the Gibbs free energy of the entire reaction step for HER. Besides, the self-supported catalysts of Co-WS2 nanoparticles confining 1D nanofibers exhibit an increased number of active sites. As expected, the heterostructure Co-WS2 catalysts exhibit remarkable HER activity with an overpotential of 113 mV to reach 10 mA cm−2 and stability with 30 h catalyzing at 23 mA cm−2. This work can provide an avenue for designing highly efficient catalysts applicable to the field of energy storage and conversion.

VOx-doped CoP catalysts with synergistic dual-active configuration for boosting hydrogen evolution kinetics

Hydrogen evolution reaction (HER), is of great significance to harvest H2 via energy-saving alkaline water electrolysis yet still challenging. Integrating heterogeneous materials is effective in designing favorable electrocatalysts for water dissociation (WD) and H-immediate involved adsorption/desorption behavior and triggering positive interactions to break the kinetics limitation. Herein, a promising configuration of a vanadium-oxide species integrated with cobalt-phosphide plane that grown on the nickel foam (labeled as VOx-CoP/NF), is demonstrated to boost the alkaline HER kinetics comprehensively. The doped vanadium-oxide species preferentially perform the WD process to generate H-intermediates. Meanwhile, interaction between VOx and CoP induce the electronic redistribution that optimizes 3d-2p orbital hybridization state, which balances the adsorption strength of H* to facilitate the hydrogen transfer and enrichment. Eventually, VOx-CoP/NF exhibits supereminent alkaline HER performance with an overpotential of only 65/245 mV at 10/400 mA cm−2, superior to individual CoP and most representative cobalt-phosphide candidates. A flowing anion exchange membrane (AEM) urea-assisted water electrolyzer with VOx-CoP/NF as a bifunctional catalyst, is assembled and achieves a satisfactory performance, verifying its practical feasibility for efficient H2 production. The concept exemplified in this work is that synchronous optimization of elementary reaction step kinetics of HER through reasonable constructing well-defined configuration is instructive for the design of HER electrocatalysts.

Insights into the hydrolysis/alcoholysis/ammonolysis mechanisms of ethylene naphthalate dimer using density functional theory (DFT) method

Hydrolysis, alcoholysis and ammonolysis are viable routes for the efficient degradation and recycling of polyethylene naphthalate (PEN) plastic waste. Various possible hydrolysis/alcoholysis/ammonolysis reaction pathways for the degradation mechanism of the ethylene naphthalate dimer were investigated using the density functional theory (DFT) B3P86/6–31++G(d,p). To determine the thermodynamic and kinetic parameters, geometric structure optimization and frequency calculation were performed on a range of intermediates, transition states, and products associated with the reaction. The calculation results show that the highest energy barrier of the main element reaction step in hydrolysis is about 169.0 kJ/mol, the lowest is about 151.0 kJ/mol for ammonolysis, and the second is about 155.0 kJ/mol for alcoholysis. The main hydrolysis products of the ethylene naphthalate dimer are 2,6-naphthalenedicarboxylic acid and ethylene glycol; the main products of alcoholysis are dimethyl naphthalene-2,6-dicarboxylate and ethylene glycol, and the main products of ammonolysis are naphthalene-2,6-dicarboxamide and ethylene glycol. Furthermore, in the process of ethylene naphthalate dimer hydrolysis/alcoholysis/ammonolysis, the decomposition reaction in the NH3 atmosphere is better than that in methanol, and the reaction in CH3OH is better than that in the H2O molecular environment, and the increase in reaction temperature can increase its spontaneity. Our study presents the molecular mechanism of PEN hydrolysis/alcoholysis/ammonolysis and provides a reference for studying the degradation of other plastic wastes.

Elucidating reaction mechanisms in the oxidative depolymerization of sodium lignosulfonate for enhancing vanillin production: A Density Functional Theory study

Lignin is a vital organic constituent of plant biomass and it can be transformed into value-added chemicals through chemical processes. This study employs the Density Functional Theory (DFT) to investigate the mechanistic effects of various oxidants on the depolymerization of sodium lignosulfonate model compounds into vanillin. Under alkaline conditions, OH- ions participation in the hydrolysis of β-O-4 bonds has been predicted. The dehydration of dihydroconiferyl alcohol to form eugenol, with an energy barrier of 69.0 kcal/mol was identified as the major rate-determining step in the oxidation reaction. In the absence of an oxidant, the energy barrier for the oxidation of eugenol to vanillin was 77.8 kcal/mol. However, when using nitrobenzene or H2O2 as oxidants, the energy barrier has significantly decreased to 12.6 kcal/mol and 21.4 kcal/mol, respectively. The effects of temperature and pressure on the rate-determining step of the reaction were analyzed using Statistical Product and Service Solutions (SPSS) software. These results have demonstrated that the energy barrier for the hydrolysis reaction's rate-determining step is positively correlated with temperature but negatively correlated with pressure. These theoretical findings would potentially help in designing the experiments and aid in enhancing the selectivity and yield of vanillin.

Tandem catalysis of furfural to γ-valerolactone over polyoxometalate-based metal-organic frameworks: Exploring the role of confinement in the catalytic process

Polyoxometalate-based metal-organic frameworks (POMOFs) with bifunctional Lewis-Brønsted acid were designed by confining polyoxometalates (POMs: phosphotungstic acid (PW), phosphomolybdic acid (PMo) or silicotungstic acid (SiW)) within the Zr-MOFs. The confined POMs not only have their own Brønsted acid, but can also regulate the Lewis acid strength of the POMOFs via charge regulation, ultimately allowing the POMOFs to display superior catalytic performance in the tandem catalysis of furfural (FAL) to γ-valerolactone (GVL). Among the three catalysts (POMOF-PW, POMOF-PMo and POMOF-SiW), a complete conversion of FAL was achieved, while POMOF-PW exhibited the highest GVL yield (58.1 %) at 160 °C within 23 h. The leaching experiment and structural characterization of the catalyst before and after recycling confirmed the stability of the catalyst structure. The humin originates from the polymerization of furan ring-containing compounds driven by Brønsted acid. The adsorption configuration of the substrate molecules on the catalyst offers a new explanation for the tandem reaction process, i.e. that perpendicular adsorption performs only the first step of the tandem reaction, while the coexistence of perpendicular and horizontal adsorption permits the entire reaction process. This work gives unique insights into the tandem reaction of FAL and can guide the design of efficient tandem reaction catalysts.

Detoxifying bacterial genes for deoxynivalenol epimerization confer durable resistance to Fusarium head blight in wheat.

Fusarium head blight (FHB) and the presence of mycotoxin deoxynivalenol (DON) pose serious threats to wheat production and food safety worldwide. DON, as a virulence factor, is crucial for the spread of FHB pathogens on plants. However, germplasm resources that are naturally resistant to DON and DON-producing FHB pathogens are inadequate in plants. Here, detoxifying bacteria genes responsible for DON epimerization were used to enhance the resistance of wheat to mycotoxin DON and FHB pathogens. We characterized the complete pathway and molecular basis leading to the thorough detoxification of DON via epimerization through two sequential reactions in the detoxifying bacterium Devosia sp. D6-9. Epimerization efficiently eliminates the phytotoxicity of DON and neutralizes the effects of DON as a virulence factor. Notably, co-expressing of the genes encoding quinoprotein dehydrogenase (QDDH) for DON oxidation in the first reaction step, and aldo-keto reductase AKR13B2 for 3-keto-DON reduction in the second reaction step significantly reduced the accumulation of DON as virulence factor in wheat after the infection of pathogenic Fusarium, and accordingly conferred increased disease resistance to FHB by restricting the spread of pathogenic Fusarium in the transgenic plants. Stable and improved resistance was observed in greenhouse and field conditions over multiple generations. This successful approach presents a promising avenue for enhancing FHB resistance in crops and reducing mycotoxin contents in grains through detoxification of the virulence factor DON by exogenous resistance genes from microbes.

Optimal Oriented External Electric Fields to Trigger a Barrierless Oxaphosphetane Ring Opening Step of the Wittig Reaction.

The Wittig reaction is one of the most important processes in organic chemistry for the asymmetric synthesis of olefinic compounds. In view of the increasingly acknowledged potentiality of the electric fields in promoting reactions, here we will consider the effect of the oriented external electric field (OEEF) on the second step of Wittig reaction (i. e. the ring opening oxaphosphetane) in a model system for non-stabilized ylides. In particular, we have determined the optimal direction and strength of the electric field that should be applied to annihilate the reaction barrier of the ring opening through the polarizable molecular electric dipole (PMED) model that we have recently developed. We conclude that the application of the optimal external electric field for the oxaphosphetane ring opening favours a Bestmann-like mechanism.