ACS Catalysis 最新文献

{"title":"Photoinduced Iron-Catalyzed Aryl Ester Synthesis via C(sp2)-O Cross-Coupling of Carboxylic Acids with Anisoles","authors":"Jaya Tripathi, Anuj Sharma","doi":"10.1021/acscatal.5c04512","DOIUrl":"https://doi.org/10.1021/acscatal.5c04512","url":null,"abstract":"An efficient method for the synthesis of aryl esters was developed using photoinduced iron catalysis. The carboxylation of abundantly available anisoles proceeds via an aromatic radical substitution pathway. A broad range of carboxylic acids and anisoles were successfully coupled to afford aryl esters in moderate to good yields. Mechanistic studies revealed that (i) Fe(III) is reduced to Fe(II) along with the generation of a chloride radical through a visible-light-induced ligand-to-metal charge transfer (LMCT) process; (ii) the carboxy radical is formed via hydrogen atom transfer (HAT) from the carboxylic acid to the chloride radical; (iii) Fe(III) promotes <i>ipso</i>-substitution by interacting with the electronegative oxygen atom of the anisole to facilitate the aryl esters synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"109 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities","authors":"Huston Locht, David S. Potts, Zahra Rangoonwala, David W. Flaherty","doi":"10.1021/acscatal.5c04379","DOIUrl":"https://doi.org/10.1021/acscatal.5c04379","url":null,"abstract":"The structures of nucleophilic reactants affect their coordination behavior among solvent molecules and kinetics of reactions with surface intermediates within the confines of fluid-filled pores of zeolites and other microporous materials. Consequently, rates and regioselectivities of diverse chemistries may depend sensitively on nucleophile identity in manners not observed for classic fluid phase reactions. Here, we examine the impact of varying the primary alcohol (ROH) chain length on the kinetics of 1,2-epoxybutane (C₄H₈O) ring-opening within Brønsted (Al-BEA) and Lewis acid (Zr-BEA) zeolites. Turnover rates increase by factors of ∼6 (Al-BEA) and 4-fold (Zr-BEA) between methanol and 1-hexanol, yet the reaction mechanisms remain comparable. Despite modest rate differences, apparent activation enthalpies calculated from rates and activities of solvated reactants decrease linearly by 12 (Al-BEA) to 33 kJ mol^–1 (Zr-BEA) with increased proton affinity, which suggests bond formation energies for the nucleophile strongly influence rate increases. The molecular interpretation of these trends demonstrates, however, that the solvation of ring-opening transition states by zeolite pore structures and solvent molecules also governs rates. The impact of local solvating interactions appears most directly as changes in regioselectivities, which tend to enhance terminal alcohol formation with increasing ROH chain length. Regioselectivities largely do not vary with differences in fluid composition for a given ROH. The addition of H₂O increases the number of hydrogen bonds among reactive species, and trends in regioselectivities imply that the decreased hydrogen bonding ability of longer chain ROH, and not the nucleophile strength or steric bulk, determines the regioselectivities of the resulting products. This work provides direct experimental evidence that nucleophilicity and hydrogen bonding influence reaction barriers and regioselectivities in zeolite-catalyzed epoxide ring-opening, offering pathways to better control reaction kinetics.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cu–Ga Interactions and Support Effects in CO2 Hydrogenation to Methanol Catalyzed by Size-Controlled CuGa Nanoparticles Deposited on SiO2 and ZnO","authors":"David Kordus, Janis Timoshenko, Núria J. Divins, See Wee Chee, Eduardo Ortega, Mauricio Lopez Luna, Uta Hejral, Ane Etxebarria, Beatriz Roldan Cuenya","doi":"10.1021/acscatal.5c03414","DOIUrl":"https://doi.org/10.1021/acscatal.5c03414","url":null,"abstract":"Growing environmental concerns have led to a need for the reduction of CO₂ emissions and the search for alternative fuels. The synthesis of methanol via the CO₂ hydrogenation reaction provides a promising approach for these tasks. Promoting the existing Cu-based catalysts with Ga might be an option to create more effective catalysts. Here, size-controlled bimetallic CuGa nanoparticles (NPs) supported on either SiO₂ or ZnO were synthesized to study the nature of the interaction of Cu and Ga. Operando spectroscopy and diffraction characterization methods (XPS, XAS, XRD) were employed to establish structure, chemical composition, and reactivity correlations. We find that Ga stays oxidized under the reaction conditions and segregates to the surface. For the CuGa NPs/ZnO, the dominating interaction of Cu with ZnO inhibits the promoting effect of Ga. Only on the inert SiO₂ support, the beneficial influence of Ga is visible. Furthermore, high pretreatment temperatures were found to result in a favorable Cu–Ga interaction by partially reducing Ga, which is beneficial for methanol selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"114 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Cobalt-Catalyzed Cross-Electrophile Coupling of Alcohols and Trifluoroalkenes via Simultaneous C–F and C–O Bond Cleavage","authors":"Prashant S. Shinde, Valmik S. Shinde, Chen Zhu, Magnus Rueping","doi":"10.1021/acscatal.5c05140","DOIUrl":"https://doi.org/10.1021/acscatal.5c05140","url":null,"abstract":"We report an efficient cross-electrophile coupling strategy for the synthesis of <i>gem</i>-difluoroalkenes from readily available benzyl alcohols and α-trifluoromethyl alkenes. This deoxygenative/defluorinative transformation proceeds via the simultaneous cleavage of strong C–O and C–F bonds under mild electrochemical conditions, generating highly reactive benzyl radicals in situ. The methodology eliminates the need for multistep alcohol preactivation protocols and exhibits a broad substrate scope with functional group tolerance. Its synthetic utility is further demonstrated by gram-scale reactions and the late-stage functionalization of complex molecules. Given the ubiquity of alcohols and the importance of <i>gem</i>-difluoroalkene motifs in pharmaceutical and materials chemistry, this protocol offers a practical and scalable platform for C–C bond formation via radical cross-electrophile coupling.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"98 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reprogramming the Catalytic Pocket of Baeyer–Villiger Monooxygenase for Environmentally Compatible Synthesis of a Chiral Sulfoxide Pharmaceutical","authors":"Chen Zhao, Qiang Geng, Kun Shi, Jiang Pan, HuiLei Yu","doi":"10.1021/acscatal.5c06238","DOIUrl":"https://doi.org/10.1021/acscatal.5c06238","url":null,"abstract":"Proton pump inhibitors such as (<i>R</i>)-lansoprazole are essential for gastric disease treatment, yet conventional syntheses rely on environmentally hazardous transition metal catalysts. Here, we reprogrammed a Baeyer–Villiger monooxygenase from <i>Cupriavidus basilensis</i> (<i>Cb</i>BVMO) to enable environmentally compatible synthesis of (<i>R</i>)-lansoprazole from lansoprazole sulfide. By a four-amino-acid scanning strategy, a total of four variants from three residue sites exhibiting a &gt;3-fold increase in specific activity were identified. Among them, a single mutant L315Y achieved a 15-fold increase in the specific activity. Computational studies revealed that L315Y stabilizes the catalytic transition state via π–π interactions with R312, resulting in the reduction of activation energy. Subsequent combinatorial mutagenesis yielded optimized variant <i>Cb</i>BVMO_V3 with an over 30-fold increase in activity, reaching 11.6 U/mg. Following process optimization, this variant exhibited strong catalytic performance in a 4 L-scale biotransformation, achieving 97% conversion of lansoprazole sulfide (50 g/L) within 8 h. This biocatalytic route reduces the environmental factor from 62.6 to 4.75 kg_waste/kg_product and lowers the production cost by 80% compared to the chemical method. By eliminating toxic metal catalysts and minimizing waste generation, our work adds further evidence that engineered BVMOs are environmentally benign alternatives for synthesizing chiral sulfoxide pharmaceuticals.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"36 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pd-Catalyzed Asymmetric Allenylation of Secondary Phosphine Oxides with Enyne-Type Propargylic Carbamates for the Construction of Chiral Allenyl Phosphine Oxides","authors":"Yujie Dong, Nianci Zhang, Fazhou Yang, Jinbao Wang, Bo Wang, Jun Liu, Bing Zheng, Cheng Zhang, Leijie Zhou, Hongchao Guo","doi":"10.1021/acscatal.5c05571","DOIUrl":"https://doi.org/10.1021/acscatal.5c05571","url":null,"abstract":"Chiral allenyl phosphine oxides represent a significant kind of synthetic target with promising potential for various applications. However, explorations toward their asymmetric synthesis remain scarce, primarily due to the competitive coordination of phosphine oxides with metal catalysts. Herein, we report a Pd-catalyzed enantioselective allenylation of secondary phosphine oxide for the efficient construction of a variety of chiral allenyl phosphine oxides. The success of this reaction arises from the enhanced (bidentate form) coordination of a newly designed, fungicide-inspired enyne-type propargylic carbamate with a chiral Pd complex. This protocol features high yields and enantioselectivities, scalability, and versatile derivatization. Mechanistic studies confirmed the exclusion of a kinetic resolution pathway.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"53 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts","authors":"Benjamin M. Moskowitz, Jisue Moon, Yuanyuan Li, Yongqiang Cheng, Luke L. Daemen, Lane Lee, Victor Fung, Aditya Savara, Anatoly I. Frenkel, Zili Wu, Israel E. Wachs","doi":"10.1021/acscatal.5c03430","DOIUrl":"https://doi.org/10.1021/acscatal.5c03430","url":null,"abstract":"Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with <i>in situ</i> spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH₃-TPD), and DFT calculations revealed that the supported ZnO_<i>x</i> phase was present as isolated surface ZnO_<i>x</i> sites on SiO₂, with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO)₂Zn²⁺O₂Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO_<i>x</i> sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH)⁺Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH)⁺Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO)₂Zn²⁺O₂Si= sites were inactive. Greater heterogeneity among all surface ZnO_<i>x</i> sites, as assessed by <i>in situ</i> DR UV–vis spectroscopy, was associated with a greater number of ZnO_<i>x</i> sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO_<i>x</i> sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO)₂Zn²⁺O₂Si= sites on the silica support caused a greater number of active surface ZnO_<i>x</i> sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH)⁺Si) sites. Such findings suggested that inactive surface ZnO_<i>x</i> sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Investigation of the PazB-Catalyzed Cyclopropanation Reaction: Role of Active-Site Water in SN2 Mechanism","authors":"Shenggan Luo, Yike Zou","doi":"10.1021/acscatal.5c03122","DOIUrl":"https://doi.org/10.1021/acscatal.5c03122","url":null,"abstract":"We investigated the mechanism of PazB, a PLP-dependent enzyme involved in the biosynthesis of the cyclopropyl group in Pazamine, using DFT calculations, classical MD, and QM(GFN2-xTB)/MM/MD simulations. We found that two active-site water molecules selectively stabilize the rate-determining S_N2 transition state over the reactant and product states by forming hydrogen bonds with the leaving chloride. Our studies reveal the structure and function of active site water molecules. Additionally, we found that PazB significantly enhanced the population of the reactive conformation, increasing its population from 29.6% in water to 92.4% in the enzyme’s active site.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ligand-Controlled Regiodivergent Hydrosilylation of α,β-Unsaturated Esters","authors":"Zi-Lu Wang, Jin-Bo Zhao, Yun-He Xu","doi":"10.1021/acscatal.5c04323","DOIUrl":"https://doi.org/10.1021/acscatal.5c04323","url":null,"abstract":"Silyl-substituted esters have attracted considerable interest owing to their versatile reactivity. However, current methods typically use reactive organometallics and require multiple steps, with low atom economy and narrow substrate scope. These issues limit the utility of such compounds, especially those bearing hydrogen-containing silyl groups. Herein, we present a copper-catalyzed, regioselective hydrosilylation of α,β-unsaturated esters that enables efficient and tunable access to both α- and β-silyl esters bearing Si–H functionalities. In the presence of dppm as the ligand, undesired reduction pathways are effectively suppressed, affording α-silyl esters in high yields with excellent regioselectivity. Notably, this protocol is compatible with both dihydrosilanes and trihydrosilanes, marking the first example of α-silylation of α,β-unsaturated esters using trihydrosilanes. In contrast, employing dcype as the ligand promotes an <i>anti</i>-Michael-type addition, delivering β-silyl esters via an unusual α-addition of Cu–H to the α,β-unsaturated system. Deuterium-labeling studies support the involvement of a distinct α-addition mechanism. Density functional theory (DFT) calculations pinpointed the stabilizing role of the weak C–H···π interaction between the dcype ligand and the aryl ring of the substrate in the regioselectivity reversed racemic β-silylation that reversed the trend to slightly favor the β-selectivity, a trend that is augmented by solvent and temperature effects.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"50 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Creating a Microenvironment in an Amine Solution for Integrated CO2 Capture and Electroreduction","authors":"Teng Xu, Guilin Yin, Fengyu Wang, Fan Yang, Junli Xu, Jinyu Ye, Danfeng Wu, Xiaoxu Duan, Weng Fai Ip, Sen Lin, Haifeng Xiong","doi":"10.1021/acscatal.5c05334","DOIUrl":"https://doi.org/10.1021/acscatal.5c05334","url":null,"abstract":"Integrated CO₂ capture and electrochemical utilization (ICCU) is promising for decarbonization by bypassing energy-intensive desorption/compression steps compared to conventional CO₂ capture and utilization (CCU) systems. However, the critical barrier in ICCU is the mass transfer limitations of carbon-containing species from amine solutions to electrode surfaces, leading to a low CO₂ conversion and a high hydrogen evolution reaction (HER). To address this issue, we introduce an interfacial engineering strategy to create a microenvironment using quaternary ammonium cationic surfactants for enhanced CO₂ conversion. In the cetyltrimethylammonium bromide (CTAB)-modified monoethanolamine (MEA) system, a Ag nanoparticle achieved 63.4% CO Faradaic efficiency at −0.82 V vs RHE, representing a 4.7-fold improvement over unmodified system. Chain-length optimization revealed that short-chain surfactants lacked sufficient hydrophobicity, while long-chain variants increased the mass transfer resistance, positioning CTAB (C₁₆) as the optimal candidate. The strategy demonstrates amine versatility and 50 h of recyclability without catalyst/amine degradation. In situ spectra and density functional theory calculation elucidated that CTAB has dual roles, i.e., CTAB cation (CTA⁺) adsorption repels the aggregation of protonated amine (MEAH⁺) on the electrode surface and the hydrophobic alkyl chains enrich the carbon-containing species. This work provides a mechanistic framework for designing efficient and stable ICCU systems through creating a microenvironment.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}