ACS Catalysis 最新文献

{"title":"Boosting Visible-Light Photocatalytic Syngas Production via Spatially Adjacent Dual Sites of Co Metal and Sulfur Vacancy in ZnIn2S4","authors":"Bin Liu, Xi Zhou, Hao Ma, Xianli Hu, Ruimei Fang, Wei Xu, Fan Dong","doi":"10.1021/acscatal.5c05481","DOIUrl":"https://doi.org/10.1021/acscatal.5c05481","url":null,"abstract":"Solar-driven conversion of CO₂ to syngas (CO/H₂) represents a promising approach for carbon-neutral fuel synthesis. However, achieving efficient and selective photocatalytic CO₂ reduction remains challenging due to competition from the hydrogen evolution reaction (HER) and inadequate spatial control over active site distribution. Herein, we introduce a Co-doped ZnIn₂S₄ (CoZIS) photocatalyst, where Co doping induces the formation of adjacent Co metal sites and sulfur vacancies (Vs), establishing spatially coordinated dual active sites. This architecture enables selective CO₂ adsorption and activation at Co sites via d-p orbital hybridization coupled with proton reduction at neighboring Vs, thereby promoting proton-coupled electron transfer (PCET) and facilitating *COOH intermediate formation. The optimized CoZIS delivers a syngas production rate of 1314.8 μmol g^–¹ h^–¹ under visible-light irradiation, surpassing reported yields for many analogous sulfide-based photocatalysts. In-situ spectroscopic studies, kinetic isotope effect (KIE) experiments, and density functional theory (DFT) calculations demonstrate that the proximity of Co and Vs sites reduces the *COOH formation energy barrier while improving the charge separation efficiency. This work advances a versatile dopant-defect engineering strategy for creating synergistic dual sites that orchestrate CO₂ and proton reduction, offering broad implications for syngas production and carbon recycling technologies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145283767","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":"Interface Engineering Induced by Potassium-Intercalated Graphite on Co3O4 for Selective Electrooxidation of Glycerol into Glycolate","authors":"Sheng Zhong, Shuang Wei, Bin He, Ruirui Wang, Syed Ali Haider Zaidi, Hasnain Nawaz, Haozhan Chu, Ruixia Liu","doi":"10.1021/acscatal.5c05731","DOIUrl":"https://doi.org/10.1021/acscatal.5c05731","url":null,"abstract":"Transforming glycerol into glycolic acid through electrocatalysis offers a strategy for valorizing surplus glycerol and alleviating the energy dilemma. However, it remains challenging to precisely control the oxidation of the hydroxyl functional group and the fracture of the C–C bond. Herein, we develop an interface engineering strategy utilizing potassium graphite intercalation compounds (K-GIC) to modulate Co₃O₄, achieving significantly enhanced performance in producing glycolate from the electrocatalytic glycerol oxidation reaction (GOR). Specifically, the interfacial charge transfer from electron-rich KC_<i>x</i> to Co₃O₄ increases the electronic density of Co and O atoms. Meanwhile, more oxygen vacancies were generated on Co₃O₄ due to the electronic effect and lattice distortion. Consequently, the markedly enhanced adsorption capacities and modulated adsorption ratio of glycerol and reactive oxygen species OH^– are determined on the catalytic interface. As a result, while the surface catalytic activity is enhanced, the deep oxidation of glycerol and secondary C–C cleavage are weakened, which is beneficial for the generation of glycolate. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations further unlock the decrease in the energy barrier in the pathway toward glycolate. The KC_<i>x</i>-Co₃O₄ exhibits high glycolate selectivity and faradaic efficiency, reaching 44% and 37%, respectively, with a glycerol conversion of 97%. This work provides practical guidance for interface engineering in designing catalysts for value-added glycerol electrooxidation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"340 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145283864","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":"Efficient Artificial Cu(II)-Diels–Alderase Based on Streptavidin for Highly Enantio- and Regioselective Diels–Alder Reactions","authors":"Yong Tang, Yongqi Zeng, Chunyu Wang, Zhi Wang, Danning Zhao, Chuang Du, Fengxi Li, Lei Wang","doi":"10.1021/acscatal.5c06248","DOIUrl":"https://doi.org/10.1021/acscatal.5c06248","url":null,"abstract":"The enzymatic Diels–Alder reaction presents an environmentally appealing strategy for synthesizing chiral norbornene scaffolds. In this study, an artificial Diels–Alderase was constructed by incorporating a biotinylated Cu-phenanthroline cofactor (5-NH₂Phen-biotin*Cu(NO₃)₂) into streptavidin and optimizing the enzyme through genetic engineering. The S112D variant of this artificial Diels–Alderase exhibited commendable catalytic performance, facilitating highly enantio- and regioselective Diels–Alder reactions. Employing this method, we synthesized a series of norbornene pyridones with broad substrate scopes and good functional group tolerance under mild conditions, achieving high yields along with good enantio- and regioselectivities. Molecular dynamics (MD) simulations provided insights into the critical complex intermediates involved in the proposed reaction mechanism and clarified the interactions between the Diels–Alderase and its substrates, revealing the structural basis for the generation of the predominant norbornenepyridone conformation and the enhanced selectivity observed with the S112D mutant. Furthermore, quantum mechanics/molecular mechanics (QM/MM) calculations analyzed the reaction energy barriers of possible transition states, elucidating the reason for the formation of the target product from an energetic perspective.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"19 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145283766","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":"How Cation Size Modulates the Anion Effect in CO2 Electroreduction: Insights from Multiscale Modeling of Electrochemical Interfaces","authors":"Ke Ye, Yulan Han, Fan Wu, Xiran Cheng, Zhiyao Duan, Guozhen Zhang, Peijun Hu, Maårten S. G. Ahlquist","doi":"10.1021/acscatal.5c04787","DOIUrl":"https://doi.org/10.1021/acscatal.5c04787","url":null,"abstract":"The interplay of cations and anions within the electric double layer (EDL) under an applied potential is crucial for the activity and selectivity of CO₂ electroreduction (eCO₂RR). Yet, first-principles level modeling of the EDL’s complex structure on large spatiotemporal scales remains challenge. Here, we combine grand canonical ensemble density functional theory with classical molecular dynamics to investigate ion effects under constant potential. Our simulation revealed a critical yet subtle link between cation and anion effects, uncovering an unexpected mechanism for the known size-dependent cation effects. We found that cation modulation of near-surface anion distribution, rather than direct intermediate stabilization of a *COO^– intermediate, is the dominant factor. Larger cations, such as Cs⁺, more effectively shield anions from the cathode and thereby reduce their inhibition of CO₂ adsorption. Our operando-mimicking simulations not only reveal the multiple roles of alkali metal cations in eCO₂RR through their hydration dynamics and anion shielding effects but also provide insight into their size dependence, guiding the precise modulation of EDL for enhanced eCO₂RR performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"338 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145261342","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":"Active Center Inheritance: A Design Principle for Constructing Atomically Dispersed Bimetallic OER/ORR Catalysts Derived from Single-Atom Catalysts","authors":"Wenwen Li, Yiming Mo, Lingzhi Kang, Caixia Li, Jingnan Zheng, Chenglong Qiu","doi":"10.1021/acscatal.5c04004","DOIUrl":"https://doi.org/10.1021/acscatal.5c04004","url":null,"abstract":"Atomically dispersed bimetallic catalysts (ADCs), an emerging class of electrocatalysts, combine the synergistic advantages of dual-metal active sites with the atomic dispersion and high metal utilization efficiency characteristic of single-atom catalysts (SACs). Their unique structural features offer the potential to exceed the catalytic performance of conventional systems but simultaneously pose challenges due to the absence of well-established rational design principles. This paper proposes and validates a structural design strategy, “Active Center Inheritance,” wherein high-performance SACs are transformed into ADCs by retaining the same active center (M–N<i>x</i>). This approach not only preserves high catalytic activity but also significantly reduces the computational cost associated with density functional theory (DFT) calculations over 13,500 candidate systems, thereby accelerating the discovery of bifunctional electrocatalysts. A total of 17 high-performance oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) bifunctional catalysts were identified through this strategy. This strategy was successfully generalized to three other ADC structural systems with different spatial arrangements. Moreover, a unified descriptor (φ), composed of four key electronic and atomic features, was constructed to effectively correlate the adsorption behaviors of critical reaction intermediates (*OH, *O, and *OOH) across diverse systems. The results reveal that SACs and ADCs can achieve comparable catalytic activity when constructed with the same M–N<i>x</i> active center, thereby enabling the synergistic optimization of active sites. This work provides a theoretical basis and a rational design framework for the development of efficient multisite electrocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145283066","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":"Stable Electrothermal Reforming of Undiluted CH4/CO2 by Integrating Encapsulated Ni Nanoparticles with Internal Joule Heating","authors":"Xiaoqiang Huang, Jingwen Chu, Yanru Zhu, Jingrou Ye, Chengeng Li, Jing He, Xue Duan","doi":"10.1021/acscatal.5c04632","DOIUrl":"https://doi.org/10.1021/acscatal.5c04632","url":null,"abstract":"Methane dry reforming (DRM) serves as a promising solution for mitigating carbon emission by valorizing two greenhouse gases (GHGs), methane and carbon dioxide, into value added syngas. However, the industrialization of DRM is practically hindered by extreme energy consumption, rapid coke formation, and severe metal sintering. All three limitations rooted in the high operation temperature required for overcoming the strong reaction endothermicity (Δ<i>H</i> = 247 kJ/mol). Herein, we presented an approach to address these bottlenecks via a highly efficient and stable electrothermal DRM (EDRM) process employing solely electricity-induced heat (Joule heating) as the heat source and adopting highly active structured Ni-embedded zeolite as catalysts. Using undiluted mixture of CH₄ and CO₂ as feedstock, EDRM exhibited superior space-time yield of syngas (17850 L_syngas/(g_Ni h)) that surpassed the documented conventional DRM with Ni-based catalysts, together with a remarkable stability during 330 h time on stream at 800 °C without observable deactivation or coke deposition. The high activity (5.1 mmol/min) and stability were attributed to in-situ heat supply with high energy transfer efficiency (22.7%) and high resistance to temperature drop by reaction heat (less than ±3 °C), together with the embedding of Ni nanoparticles by zeolite that prevented metal from sintering. Meanwhile, mechanistic studies revealed that the high catalytic activity and stability of the Ni-embedded zeolite catalyst was achieved via a unique synergy between closely contacted silanol groups of the zeolite framework and embedded Ni particles that induced a carbonate-mediated pathway for efficient CO₂ activation and rapid carbon consumption. This study not only presented a renewable energy-driven GHGs utilization strategy with industrial scalability but also highlighted the fundamental significance of electrothermal catalysis as an emerging interdisciplinary frontier bridging electrochemistry and thermal catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255773","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":"Mechanism of Action of MAO’s Molecular Cousin","authors":"Gaia Urciuoli, Francesco Zaccaria, Cristiano Zuccaccia, Roberta Cipullo, Peter H. M. Budzelaar, Gabriel Menendez Rodriguez, Leonardo Tensi, Antonio Vittoria, Christian Ehm, Vincenzo Busico, Alceo Macchioni","doi":"10.1021/acscatal.5c05698","DOIUrl":"https://doi.org/10.1021/acscatal.5c05698","url":null,"abstract":"The aluminum-alkyl borate (AAB) salt {[<i>i</i>Bu₂(DMA)Al]₂(μ-H)}⁺[B(C₆F₅)₄]⁻ (<b>AlHAl_DMA</b>; DMA = <i>N,N</i>-dimethylaniline) is able of fully activating dichloride precatalysts for olefin polymerization and serving as an impurity scavenger, thus deserving to be called a <i>molecular cousin</i> of the well-established methylaluminoxane (MAO). With respect to MAO, it offers the advantage of having a well-defined molecular structure, which was exploited herein to investigate its mechanism of action as a cocatalyst. Particularly, the reaction of the precatalyst (Me₂SiCp₂)ZrCl₂ with <b>AlHAl_DMA</b> and with stable [Al<i>i</i>Bu₂(L)]⁺, modeling the putative abstracting species [Al<i>i</i>Bu₂(DMA)]⁺, was studied. The latter reaction led to the isolation of a rare, singly bridged Zr–(μ-Cl)–Al heterodinuclear adduct (<b>2</b>), which is a plausible intermediate of chloride abstraction from the precatalyst. Addition of di-<i>iso</i>-butylaluminum hydride (DIBAL-H) to <b>2</b> yielded a mixture of several multinuclear Zr/Al adducts with bridging μ-Cl and μ-H fragments (<b>3–6</b>), which were fully characterized by in-depth 2D NMR spectroscopy. Analogous products were observed in the reaction between (Me₂SiCp₂)ZrCl₂ and <b>AlHAl_DMA</b>, reinforcing the hypothesis that they are intermediates of chloride/hydride exchange, which generates a polymerization-active Zr–H species. The solid-state structure of [(Me₂SiCp₂)Zr]₂(μ-H)(μ-Cl)(μ² -<i>i</i>Bu₂AlH₂) (<b>5</b>) was determined by single-crystal X-ray diffraction. The presence of the μ-H fragment in <b>AlHAl_DMA</b> appears to be relevant also for determining the excellent impurity scavenging properties of this cocatalyst, as it was found to react more rapidly than Al–<i>i</i>Bu moieties upon exposure of solutions of this cocatalyst to atmospheric oxygen and moisture.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145261429","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":"Breaking Scaling Relations with Inverse Catalysts: A Machine Learning Exploration of Trends in CO2-to-Formate Energy Barriers","authors":"Luuk H. E. Kempen, Marius Juul Nielsen, Mie Andersen","doi":"10.1021/acscatal.5c05872","DOIUrl":"https://doi.org/10.1021/acscatal.5c05872","url":null,"abstract":"The conversion of CO₂ into useful products such as methanol is a key strategy for abating climate change and our dependence on fossil fuels. Developing improved catalysts for this process is costly and time-consuming and can thus benefit from computational exploration of possible active sites. However, this is complicated by the complexity of the materials and reaction networks. Here, we present a workflow for exploring transition states of elementary reaction steps at inverse catalysts, which is based on the training of a neural network-based machine learning interatomic potential. We focus on the crucial formate intermediate and its formation over nanoclusters of indium oxide supported on Cu(111). The speedup compared to an approach purely based on density functional theory allows us to probe a wide variety of active sites found at nanoclusters of different sizes and stoichiometries. Analysis of the obtained set of transition state geometries reveals different structure–activity trends at the edge or interior of the nanoclusters. Furthermore, the identified geometries allow for the breaking of linear scaling relations, which could be a key underlying reason for the catalytic performance of inverse catalysts observed in experiments.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"40 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255775","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":"Plasma-Assisted Ammonia Synthesis from N2 and H2O over rGO-TiO2 Catalysts: Enhancing Energy Efficiency and Unraveling Reaction Mechanisms","authors":"Shilin Song,&nbsp;, ,&nbsp;Fei Wang,&nbsp;, ,&nbsp;Xin Sun,&nbsp;, ,&nbsp;Yi Chen,&nbsp;, ,&nbsp;Jiawen Liu,&nbsp;, ,&nbsp;Yanxing Shi,&nbsp;, ,&nbsp;Ping Ning,&nbsp;, ,&nbsp;Yixing Ma*,&nbsp;, and ,&nbsp;Kai Li*,&nbsp;","doi":"10.1021/acscatal.5c06041","DOIUrl":"10.1021/acscatal.5c06041","url":null,"abstract":"<p >The reduction of N₂ to ammonia (NH₃) using H₂O as a hydrogen source is a promising low-carbon alternative to the Haber–Bosch process, but the efficient dissociation of N₂ and H₂O remains a challenge. Here, a reduced graphene oxide–titanium dioxide (rGO-TiO₂) hybrid catalyst was developed to enhance H₂O and N₂ dissociation under dielectric barrier discharge (DBD) plasma, facilitating plasma-assisted ammonia synthesis. The 5-rGO-TiO₂ catalyst achieved an NH₃ formation rate of 4196.62 μmol g_cat^–1 h^–1 and a high energy efficiency of 1317.77 mg kWh^–1. Mechanistic investigations using optical emission spectroscopy (OES), in situ Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) confirmed the formation of reactive nitrogen species, NH<i>_x</i> intermediates, and NH₃, demonstrating the synergistic role of rGO in electron transfer and reactant dissociation. Density functional theory (DFT) calculations further revealed that rGO significantly lowers the energy barriers for N₂ and H₂O dissociation, improving the ammonia synthesis efficiency. Overall, the integration of rGO-TiO₂ with plasma catalysis effectively enhances reactant activation and catalytic performance, offering insights into the design of advanced catalysts for low-energy ammonia production.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 20","pages":"17603–17613"},"PeriodicalIF":13.1,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247205","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":"Copper-Catalyzed Enantioselective 1,3-Dipolar Cycloaddition Enabled by a Ketimine-Based Umpolung Strategy","authors":"Hui-Ling Qian,&nbsp;, ,&nbsp;Hong-Dan Deng,&nbsp;, ,&nbsp;Lei Yang,&nbsp;, ,&nbsp;Zhen-Hua Wang,&nbsp;, ,&nbsp;Yong You,&nbsp;, ,&nbsp;Wenjing Zhang*,&nbsp;, ,&nbsp;Wei-Cheng Yuan*,&nbsp;, and ,&nbsp;Jian-Qiang Zhao*,&nbsp;","doi":"10.1021/acscatal.5c06243","DOIUrl":"10.1021/acscatal.5c06243","url":null,"abstract":"<p >Catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides with various dipolarophiles has emerged as an efficient method for preparing pyrrolidine ring systems through normal [3 + 2] cycloadditions. However, achieving the catalytic enantioselective regio-reversed [3 + 2] cycloadditions via an imine-based umpolung strategy remains a formidable challenge. In this work, we present a copper-catalyzed umpolung of <i>N</i>-2,2,2-trifluoroethyl benzo[<i>b</i>]thiophene-2,3-dione-derived ketimines for the regio-reversed enantioselective 1,3-dipolar cycloaddition with benzo[<i>b</i>]thiophene sulfones. This strategy offers a highly regio-, diastereo-, and enantioselective approach for preparing chiral polycyclic spiro-compounds containing benzothiophenone, α-trifluoromethyl pyrrolidine, and benzosulfolane subunits, featuring four contiguous stereocenters with good results (up to 98% yield, all cases &gt;20:1 dr and &gt;99% ee). Density functional theory computational studies shed light on the reaction mechanism and the origin of the stereoselective control in this regio-reversed cycloaddition. The practicality and versatility of the methodology were also demonstrated by scale-up experiments and different transformations of the product.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 20","pages":"17591–17602"},"PeriodicalIF":13.1,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247206","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}