ACS Catalysis 最新文献

{"title":"Direct Synthesis of N-Fused Indoles Enabled by Copper-Catalyzed Aerobic Oxygenative Rearrangement","authors":"Yan-Zheng Sun, Hu-Cheng Yang, Jun-Rong Song, Hong-Yu Li, Jun Shi, Biaobiao Jiang, Chao Chen, Wei Wu, Hai Ren","doi":"10.1021/acscatal.4c05762","DOIUrl":"https://doi.org/10.1021/acscatal.4c05762","url":null,"abstract":"<i>N</i>-Fused indoles are typical <i>N</i>-heterocycles, which are extensively found in natural products and bioactive molecules. Despite their importance, the synthesis of N-fused indoles has not yet been fully developed. Herein, we report a direct, general unified copper-catalyzed aerobic oxygenative skeletal rearrangement strategy using readily available cyclic indole substrates, which provides a practical synthetic platform for the rapid construction of a wide array of N-fused indole scaffolds. This open-flask method features mild reaction conditions, high chemoselectivity, and a broad substrate scope (over 90 examples). The scaled-up synthesis and versatile transformations of the products using various nucleophiles demonstrated the scalability and utility of this protocol. Mechanistic studies revealed that, by involving a unique single-electron transfer (SET)-induced aerobic oxygenation mechanism, the reaction of tetrahydro-γ-carbolines proceeded via a formal 1,3-migration rearrangement, while that of tetrahydrocarbazoles proceeded by a Witkop–Winterfeldt/C–C cleavage cascade.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579842","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 B–H Aryl/Alkenylation of 1,2-Azaborines","authors":"Zhen Zhang, Dandan Jiang, Peiwen Su, Kai Yang, Peiyuan Yu, Qiuling Song","doi":"10.1021/acscatal.4c04576","DOIUrl":"https://doi.org/10.1021/acscatal.4c04576","url":null,"abstract":"Direct functionalization of 1,2-azaborines to construct B–C bonds remains challenging. Here, we report a Pd-catalyzed B–H aryl/alkenylation reaction of 1,2-azaborines. The method provides a general platform to access diverse boron-substituted 1,2-azaborine compounds (&gt;60 examples). The synthetic utility is highlighted through the late-stage modification of bioactive molecules, as well as the preparation and transformations of the ¹⁰B-enriched 1,2-azaborine product and the synthesis of four BN isostere analogues of bioactive molecules. And the reaction mechanism is also explored and discussed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574619","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":"Nickel-Catalyzed Atroposelective Reductive [2 + 4] Annulation toward Synthesis of Axially Chiral Biaryls","authors":"Yujia Mao, Weitao Hu, Chuan Wang","doi":"10.1021/acscatal.4c06131","DOIUrl":"https://doi.org/10.1021/acscatal.4c06131","url":null,"abstract":"Herein, we demonstrate the successful application of reductive [2 + 4] annulation in the atroposelective de novo benzene ring formation. This nickel-catalyzed reaction between β-substituted α-naphthylalkynes and a biselectrophile of C(sp²)–X type offers an efficient and convenient method to prepare highly enantioenriched C₁-symmetric axially chiral biaryls containing two preinstalled functionalities. The coupling products can be used as versatile synthetic intermediates to access bidentate ligands or bifunctional organocatalysts, and their utility in asymmetric catalysis is also showcased in this context.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580002","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":"Synchronous Construction of Ni/CeO2/C with Double Defects as a Dual Engine for Catalytic Refinement of Lignin Oil Under Hydrogen-Free Condition","authors":"Yingbo Zhu, Yulong Ma, Yonggang Sun, Wenxin Ji, Liqiong Wang, Feng Lin, Yuanyuan Li, Hongqiang Xia","doi":"10.1021/acscatal.4c03228","DOIUrl":"https://doi.org/10.1021/acscatal.4c03228","url":null,"abstract":"The ambiguous structural defect types and sites of catalysts impede the investigation of structure–activity relationships at the atomic scale for catalytic transfer of hydrodeoxygenation of lignin and its derivatives. In this work, oxygen vacancies (O_v) and carbon defects (C_d) in Ni/CeO₂/C catalysts were constructed by an in situ calcination atmosphere-induced engraving strategy. The dual defect embodied the chemical characteristics of heterogeneous frustrated Lewis pairs, and the synergy between O_v and C_d could effectively promote the adsorption and activation of isopropanol and the oxygen-containing substrate, which stimulated the production of more reactive H^δ+ and H^δ−, anchored the methyl group. Efficient conversion of lignin oil was achieved without initial H₂ pressure, yielding 56% liquid product and 62.9% C₆₊ cycloalkanol selectivity. The traditional hydrodeoxygenation was transformed into a solid–liquid two-phase catalytic transfer hydrodeoxygenation, which enhanced the mass transfer. This study developed a catalytic system for catalytic transfer hydrodeoxygenation and offered insights for the preparation of heterogeneous frustrated Lewis pairs.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574616","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":"Rh(III)-Catalyzed Alkene Anti Nucleoamidation to Access Diverse Heterocycles","authors":"Noah Wagner-Carlberg, Julia R. Dorsheimer, Tomislav Rovis","doi":"10.1021/acscatal.4c05499","DOIUrl":"https://doi.org/10.1021/acscatal.4c05499","url":null,"abstract":"Alkene difunctionalization methods are an attractive way to rapidly build molecular complexity by using readily available starting materials. One common approach is transition metal-catalyzed nucleometalation, which converts the C–C double bond to a C–Nu bond and a C–M bond. Commonly, a tethered nucleophile is used to form pharmaceutically relevant heterocyclic cores in this manner. The resulting alkylmetal species can then be further functionalized in a number of ways. While methods exist to aminate the C–M bond, direct installation of valuable amides is rare. Additionally, nucleometalation methods are often limited to the use of a single type of nucleophile. Herein, we disclose a general method for the Rh(III)-catalyzed nucleoamidation of alkenes, forming a variety of heterocyclic cores.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580001","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":"Boosting Solar-to-H2O2 by Molecularly Tunable Heterostructured Pym-CN with an Enhanced Built-In Electric Field","authors":"Jiayu An, Wenjun Jiang, Fuwei Zhuang, Yinhua Ma, Su Zhan, Feng Zhou","doi":"10.1021/acscatal.4c05203","DOIUrl":"https://doi.org/10.1021/acscatal.4c05203","url":null,"abstract":"Utilizing photocatalytic technology to achieve efficient production of H₂O₂ is a hot topic. Here, we synthesized a photocatalytic material with a strong built-in electric field, namely, Pym-CN, through a hydrothermal-assisted thermal polymerization strategy, which effectively promotes the separation and transfer of photoinduced charge carriers. A pyrimidine ring was successfully introduced into the heptazine structure unit of Pym-CN, which leads to electron aggregation at N═C–N, benefiting for enhancing the strong sorption and activation capabilities of oxygen. Under the condition of visible light wavelength greater than 400 nm (λ &gt; 400 nm), the H₂O₂ production rate of Pym-CN (2622.5 μmol/L/h) is 7.6 times that of the BCN. A detailed investigation of the reaction mechanism revealed that Pym-CN follows a two-step continuous process of single-electron oxygen reduction reaction (ORR). This work elucidates the application prospects of the donor–acceptor (D–A) structure with a strong built-in electric field in the field of efficient photocatalytic production of H₂O₂.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574618","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":"Harnessing Electrolyte Chemistry to Advance Oxygen Reduction Catalysis for Fuel Cells and Electrosynthesis","authors":"Yong-Yan Zhao, Wenhe Yu, Xiaoxuan Sun, Hengshuo Huang, Fengwang Li, Mingchuan Luo","doi":"10.1021/acscatal.4c05425","DOIUrl":"https://doi.org/10.1021/acscatal.4c05425","url":null,"abstract":"Oxygen reduction reaction (ORR) is ubiquitous in many important energy conversion technologies, encompassing fuel cells, metal-air batteries, and H₂O₂ electrosynthesis. However, its inherently sluggish kinetics often leads to substantial overpotentials and losses in efficiency, thus prompting extensive efforts into catalyst optimization. In the past few years, growing research has underscored the pivotal role of electrolyte-associated factors in affecting the ORR performance. In this review, we focus on the intricate interplay between electrolyte properties, pH, cations, anions, and additives, and their impacts on ORR electrocatalysis, particularly for platinum (and its alloys) and nonprecious metal–nitrogen–carbon catalysts. We examine how these electrolyte-mediated alterations affect the electrode surface, reactive species, and microenvironment, thereby modulating the adsorption energetics of intermediates, catalyst stability and mass transport, and ultimately affecting the overall ORR process. We highlight the need for dynamic models and advanced probing technologies at the electrocatalytic interfaces, and advocate for adopting a holistic approach that synchronizes effects of electrolytes and catalysts in optimizing ORR electrocatalysis. This review lays the foundation for refining descriptive formulations for ORR electrocatalysis, which potentially guides the development of enhanced ORR cathodes for practical applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566032","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":"Altering Active-Site Loop Dynamics Enhances Standalone Activity of the Tryptophan Synthase Alpha Subunit","authors":"Cristina Duran, Thomas Kinateder, Caroline Hiefinger, Reinhard Sterner, Sílvia Osuna","doi":"10.1021/acscatal.4c04587","DOIUrl":"https://doi.org/10.1021/acscatal.4c04587","url":null,"abstract":"The α-subunit (TrpA) of the allosterically regulated bifunctional tryptophan synthase αββα enzyme catalyzes the retro-aldol cleavage of indole-glycerol phosphate (IGP) to <span>d</span>-glyceraldehyde 3-phosphate (G3P) and indole. The activity of the enzyme is highly dependent on the β-subunit (TrpB), which allosterically regulates and activates TrpA for enhanced function. This contrasts with the homologous BX1 enzyme from <i>Zea mays</i> that can catalyze the same reaction as TrpA without requiring the presence of any additional binding partner. In this study, we computationally evaluated and compared the conformational landscapes of the homologous <i>Zm</i>BX1 and <i>Zm</i>TrpA enzymes. Our results indicate that enhanced TrpA standalone activity requires the modulation of the conformational dynamics of two relevant active-site loops, loop 6 and 2, that need to be synchronized for accessing the catalytically activated closed state for IGP cleavage, as well as open states for favoring indole/G3P release. Taking as inspiration the evolutionary blueprint <i>Zm</i>BX1 and using our developed correlation-based tool shortest path map focused on the rate-determining conformational transition leading to the catalytically activated closed state, we computationally designed a variant named <i>Zm</i>TrpA^SPM4-L6BX1, which displays a 163-fold improvement in catalytic efficiency for the retro-aldol cleavage of IGP. This study showcases the importance of fine-tuning the conformational dynamics of active-site loops for altering and improving function, especially in those cases in which a conformational change is rate determining.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566200","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":"Understanding Activity Trends in Electrochemical Dinitrogen Oxidation over Transition Metal Oxides","authors":"Samuel A. Olusegun, Yancun Qi, Nishithan C. Kani, Meenesh R. Singh, Joseph A. Gauthier","doi":"10.1021/acscatal.4c05036","DOIUrl":"https://doi.org/10.1021/acscatal.4c05036","url":null,"abstract":"Nitric acid (HNO₃) is a critical commodity chemical produced on an enormous scale via oxidation of ammonia NH₃ in the Ostwald process and, as such, is responsible for a significant fraction of global greenhouse gas emissions. Formation of nitric acid by direct oxidation of dinitrogen via the electrochemical nitrogen oxidation reaction (N2OR) is an attractive alternative but has so far largely remained elusive. Toward advancing our fundamental understanding of the limitations of the N2OR, in this article, we investigated the competitive adsorption dynamics of nitrogen (N₂) and water oxidation intermediates such as hydroxide (OH) on a range of transition metal oxides. Using density functional theory (DFT) calculations, we explore three possible N2OR mechanisms: direct adsorption and dissociative adsorption of N₂, and a Mars-van Krevelen (MvK)-type mechanism involving the adsorption of N₂ on a surface-bound atomic oxygen. We observed a strong linear scaling relation between the adsorption energy of N₂ and OH on the metal-terminated transition metal oxide, suggesting that under typical highly oxidizing operating conditions for the N2OR (<i>U</i>_RHE &gt; 1.24 V), water oxidation intermediates such as OH are likely to dominate the surface, leading to vanishingly small coverage of adsorbed N₂. From this result, we find that direct or dissociative adsorption of N₂ is unlikely, suggesting an MvK-type mechanism for the N2OR. Probing this mechanism further using DFT, we find that the reaction energetics are largely less favorable than water oxidation due to the high activation barrier for N₂ adsorption, which we find to be the rate-determining step for the process. Our experimental results corroborate these findings with the majority of tested catalysts exhibiting poor N2OR selectivity and a rate-determining step involving N₂(g). However, dynamic potential control emerged as a possible strategy to enhance N2OR activity as it may limit the oxygen evolution reaction (OER) and promote N₂ adsorption. This work underscores the challenges in achieving efficient N2OR, highlighting the need for unconventional catalyst designs and operational strategies, such as electrolyte engineering and dynamic potential control, to overcome the inherent kinetic and thermodynamic barriers.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561800","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":"Role of Interfacial Hydrogen in Ethylene Hydrogenation on Graphite-Supported Ag, Au, and Cu Catalysts","authors":"Thomas Wicht, Alexander Genest, Lidia E. Chinchilla, Thomas Haunold, Andreas Steiger-Thirsfeld, Michael Stöger-Pollach, José J. Calvino, Günther Rupprechter","doi":"10.1021/acscatal.4c05246","DOIUrl":"https://doi.org/10.1021/acscatal.4c05246","url":null,"abstract":"A combined surface science/microreactor approach was applied to examine interface effects in ethylene hydrogenation on carbon-supported Ag, Au, and Cu nanoparticle catalysts. Turnover frequencies (TOFs) were substantially higher for supported catalysts than for (unsupported) polycrystalline metal foils, especially for Ag. Spark ablation of the corresponding metals on highly oriented pyrolytic graphite (HOPG) and carbon-coated grids yielded nanoparticles of around 3 nm size that were well-suited for characterization by X-ray photoelectron spectroscopy (XPS), high-resolution (scanning) transmission electron microscopy (HRTEM/STEM), and energy dispersive X-ray spectroscopy (EDX). Polycrystalline metal foils characterized by scanning electron microscopy (SEM), EDX, electron backscatter diffraction (EBSD), XPS, and low-energy ion scattering (LEIS) served as unsupported references. Employing a UHV-compatible flow microreactor and gas chromatography (GC) allowed us to determine the catalytic performance of the model catalysts in ethylene hydrogenation up to 200 °C under atmospheric pressure. Compared to the pure metal foils, the HOPG-supported metal nanoparticles exhibited not only strongly increased activity but also higher stability (slower deactivation) and differing reaction orders. For the most active Ag catalysts, DFT calculations were carried out to determine the adsorption energies of the reacting species on single-crystal surfaces as well as on carbon-supported and unsupported Ag nanoparticles. Adsorption of molecular hydrogen was very weak on all unsupported Ag surfaces, resulting in hydrocarbon-“poisoned” surfaces. However, when a carbon support was present, the adsorption strength of H₂ on Ag nanoparticles increased on average by −0.5 eV, driven by changes in Ag–Ag distances near the metal–carbon three-phase boundary (whereas subsurface carbon lowers hydrogen bonding). On Cu particles, the interface effect was calculated to be somewhat weaker than for Ag particles. H₂/D₂ scrambling experiments on Ag catalysts then corroborated a facilitated hydrogen activation for carbon-supported metals. Thus, the carbon support effect is attributed to an improved hydrogen availability at the metal–carbon interface, controlling performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561989","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}