ACS Catalysis 最新文献

{"title":"Palladium-Supported Surface-Oxidized Mo2C MXenes for the Tandem Hydrogenation–Hydrogenolysis of Furfurals via Hydrogen Spillover","authors":"Yangye Hu,&nbsp;, ,&nbsp;Yong Guo,&nbsp;, ,&nbsp;Peng Huang,&nbsp;, ,&nbsp;Yicheng Peng,&nbsp;, ,&nbsp;Guoqiang Wu*,&nbsp;, ,&nbsp;Jun Du*,&nbsp;, ,&nbsp;Jun Wang,&nbsp;, and ,&nbsp;Qiang Deng*,&nbsp;","doi":"10.1021/acscatal.5c04371","DOIUrl":"10.1021/acscatal.5c04371","url":null,"abstract":"<p >Developing an efficient catalyst for the tandem hydrogenation–hydrogenolysis of furfurals to methyl furans (MFs) is crucial for synthesizing biofuels and high-value chemicals but is challenging by virtue of easy C=C hydrogenation and difficult CH₂–OH hydrogenolysis. Herein, a palladium (Pd) nanoparticle-supported surface-oxidized molybdenum carbide (Mo₂C) MXene was prepared, which exhibited a uniquely high MF yield of 92.5% from furfural at an unprecedented low temperature of 50 °C. Catalytic mechanism analysis confirmed that the hydrogen spillover from Pd nanoparticles to Mo–O sites on the MXene support generated frustrated H^δ+···H^δ− pairs that acted as atypical hydrogenation sites for the C=O hydrogenation step of furfural and as Bro̷nsted acid sites for the CH₂–OH hydrogenolysis step of furan alcohol, thereby promoting the efficient preparation of MF. Furthermore, the prepared MXene exhibited catalytic universality and extensibility for converting various furfurals, benzaldehydes, and picolinaldehydes to methyl aromatics (i.e., MFs, methylbenzenes, and methylpyridines). This study demonstrated interesting metal–acid bifunctional catalysis over a surface-oxidized MXene by triggering hydrogen spillover to form transient H^δ+···H^δ− pairs, offering a straightforward pathway for converting aromatic aldehydes to methyl aromatics.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16851–16862"},"PeriodicalIF":13.1,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089705","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":"Gas-Mediated Co Single-Atom and Co0 Synergy Driving CO2 Hydrogenation to Methanol over Co/In2O3 Catalysts","authors":"Shanshan Dang,&nbsp;, ,&nbsp;Wenqiang Zhang,&nbsp;, ,&nbsp;Chuang Gao,&nbsp;, ,&nbsp;Xiaolu Ni,&nbsp;, ,&nbsp;Zhenzhou Zhang,&nbsp;, ,&nbsp;Weifeng Tu*,&nbsp;, and ,&nbsp;Yi-Fan Han*,&nbsp;","doi":"10.1021/acscatal.5c05299","DOIUrl":"10.1021/acscatal.5c05299","url":null,"abstract":"<p >In₂O₃ modified by Co can significantly promote the catalytic activity for CO₂ hydrogenation to methanol, but there still remains a huge challenge in identifying the active sites due to variable Co phases driven by complex local environments. In this work, we find that reduction pretreatment induces Co₃O₄ to become highly dispersed, and the reduction-reaction environment leads to the formation of isolated Co sites and Co⁰ derived from a few aggregates, as confirmed by multiple surface techniques. A semiquantitative relationship between catalytic activity and surface structure clearly indicates that the synergistic sites integrating isolated Co sites and metallic Co enhance the adsorption and activation of H₂ and CO₂, thereby promoting methanol formation. The presented results imply that this reaction goes through the formate route via Co/In₂O₃. Moreover, the catalyst is stable in redox environments, and especially Co single atoms could help stabilize the surface active structure and achieve high catalytic performance.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16827–16839"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089389","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":"Mn-Catalyzed Regioselective Alkene Hydrosilylation: From Mechanism Investigation to the Design of a Pre-Catalyst Candidate","authors":"Ming-Yu Chen,&nbsp;, ,&nbsp;Naïme Soulé,&nbsp;, ,&nbsp;Alejandra Zuluaga,&nbsp;, ,&nbsp;Antoine Frot,&nbsp;, ,&nbsp;Anthony Vivien,&nbsp;, ,&nbsp;Clément Camp,&nbsp;, ,&nbsp;Chloé Thieuleux,&nbsp;, ,&nbsp;Pierre-Adrien Payard*,&nbsp;, and ,&nbsp;Marie-Eve L. Perrin*,&nbsp;","doi":"10.1021/acscatal.5c04086","DOIUrl":"10.1021/acscatal.5c04086","url":null,"abstract":"<p >The catalytic hydrosilylation of alkenes is a cornerstone process in the large-scale production of organosilicon compounds. As an alternative to precious metal catalysts, manganese-based systems such as Mn(CO)₅Br have gained significant attention due to their low cost and high availability. However, the catalytic mechanism in place is not completely understood, and several propositions have been described in the literature. To clarify this point, we have employed a combined experimental and computational approach to elucidate the activation mechanism of Mn(CO)₅Br in the anti-Markovnikov hydrosilylation of alkenes. Our findings reveal that the initiation involves specific CO ligand dissociation and substrate coordination to generate an active Mn(I) intermediate that catalyzes the desired transformation via concerted 2-electron organometallic pathways. Exploration of reaction mechanisms at the DFT level provided detailed insights into the activation mechanism of Mn(CO)₅Br, enabling the rational design of the Mn–alkyl complex Mn(CO)₅(^<i>n</i>Oct) as a precatalyst that offers direct access to the active catalytic cycle. This complex promotes anti-Markovnikov hydrosilylation of alkenes at room temperature with loadings as low as 0.5 mol % while retaining high activity and selectivity even in the presence of some contaminants.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16840–16850"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089706","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":"Elucidation of the Catalytic Apparatus and Mechanism of Human Chitotriosidase-1","authors":"Dorota Niedzialek*,&nbsp;, ,&nbsp;Grzegorz Wieczorek,&nbsp;, ,&nbsp;Katarzyna Drzewicka,&nbsp;, ,&nbsp;Anna Antosiewicz,&nbsp;, ,&nbsp;Mariusz Milewski,&nbsp;, ,&nbsp;Agnieszka Bartoszewicz,&nbsp;, ,&nbsp;Jacek Olczak*,&nbsp;, and ,&nbsp;Zbigniew Zasłona*,&nbsp;","doi":"10.1021/acscatal.5c00507","DOIUrl":"10.1021/acscatal.5c00507","url":null,"abstract":"<p >Despite extensive research over the past three decades, the catalytic mechanism of human chitotriosidase-1 (hCHIT1) has remained incompletely understood. To address this gap, we reanalyzed all available structural information and, integrating experimental data with multiscale molecular simulations, successfully modeled the full-length structure of hCHIT1 for the first time, including the previously unresolved proline-rich linker essential for domain communication. This comprehensive model enabled us to propose a general mechanism of hCHIT1 catalysis and to elucidate the distinct functional roles of all four highly conserved structural motifs of the glycoside hydrolase 18 (GH18) family, a group comprising over 65,000 known members across all domains of life. We further investigated the influence of monovalent metal ions in achieving optimal catalytic conditions and determined the activation energies for both substrate-assisted hydrolysis and transglycosylation processes. Our simulations revealed coordinated Brownian conformational fluctuations within hCHIT1 subdomains, which collectively harness thermal energy to drive catalysis. Notably, we discovered a previously unreported piston-like mechanism in which a conserved tyrosine residue transduces mechanical energy to the substrate, significantly lowering the activation barrier for catalysis. Additionally, by constructing a complete substrate model, we resolved the long-standing mechanistic enigma of the highly conserved tryptophan ‘lid’ at the active site entrance, demonstrating its multifaceted role in substrate gating, transition state stabilization, and product release. Finally, we demonstrated that binding of the first-in-class inhibitor OATD-01 induces subtle yet far-reaching dynamical changes within the active site, leading to dissociation of the immunoglobulin-like heterodimer and disruption of interactions with biological partners implicated in disease pathogenesis. These findings not only redefine the mechanistic landscape of hCHIT1 but also provide a robust framework for the rational design of next-generation GH18 inhibitors, for example, targeting multidrug-resistant pathogens.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16748–16761"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c00507","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling Electrolyte Effects on the Oxygen Reduction at Co–N–C Single-Atom Catalysts in Nonaqueous Lithium–Oxygen Batteries by Ab Initio Molecular Dynamics","authors":"Silan Chen,&nbsp;, ,&nbsp;Qinghan Yu,&nbsp;, ,&nbsp;Yujin Ji*,&nbsp;, and ,&nbsp;Youyong Li*,&nbsp;","doi":"10.1021/acscatal.5c03920","DOIUrl":"10.1021/acscatal.5c03920","url":null,"abstract":"<p >Nonaqueous lithium–oxygen batteries (LOBs) hold immense promise due to their ultrahigh theoretical energy density, yet the role of electrolytes in regulating reaction kinetics during the oxygen reduction reaction (ORR) remains fundamentally unclear. Here, we systematically explore ORR pathways at the interface between Co–N–C single-atom catalysts (SACs) and electrolytes via <i>ab initio</i> molecular dynamics (AIMD). In bulk electrolytes, simulations reveal Li⁺-solvent bonding strength follows donor number (DN) order, which may result in a difference in the free energy of interfacial reaction. High-DN solvents elevate Li⁺ insertion barrier due to strong Li⁺-solvent binding, while facilitating *LiO₂ desorption at the interface. However, the desorption of *LiO₂ into the electrolytes is found to be thermodynamically unfavorable, thereby driving the reaction toward surface-mediated growth. Low-DN electrolytes paired with high-adsorption catalysts enforce surface growth, while high-DN systems with weak-adsorption catalysts favor solution growth. Our work proposes a catalyst–electrolyte interfacial Li⁺ competition principle that governs discharge product formation pathways and offers optimization strategies for LOBs.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16782–16791"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084109","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":"Pt–Co Separation for Enhancing Bimetallic Catalysis in Selective Hydrogenation Reaction","authors":"Huibin Ge*,&nbsp;, ,&nbsp;Jiawei Yao,&nbsp;, ,&nbsp;Jinghao Fan,&nbsp;, ,&nbsp;Jian Zeng,&nbsp;, ,&nbsp;Rui Li,&nbsp;, and ,&nbsp;Yong Qin*,&nbsp;","doi":"10.1021/acscatal.5c04678","DOIUrl":"10.1021/acscatal.5c04678","url":null,"abstract":"<p >The respective role of each metal or active site is largely unexplored in bimetallic catalysts, since one metal is easily hindered or even covered by another metal. Separating the different metals by a nanoscale distance in the bimetallic catalysts can provide an opportunity to reveal their respective roles and study the synergistic mechanism. Herein, we report a yolk–shell catalyst with a Pt core and a Co shell through atomic layer deposition. Meanwhile, 1-pentanethiol is used as an isolating layer to separate the Pt core and the Co shell. In addition, the thickness is as small as 0.5 nm. In the selective hydrogenation of the cinnamaldehyde reaction, the Pt core is the active site for the decomposition of hydrogen to active hydrogen. Then the active hydrogen can spill over from the Pt surface to the Co shell for hydrogenation of the adsorbed C═O bonds. Meanwhile, the void space provides a confined space for the accumulation of active hydrogen and then further enhances the catalytic performance. Our study opens up an alternative thoroughfare to design efficient bimetallic catalysts.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16740–16747"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083949","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":"Toward Reliable and Reproducible Research in Organic Photocatalysis by Carbon Nitride","authors":"Gaia Grando,&nbsp;, ,&nbsp;Giuseppe Sportelli,&nbsp;, ,&nbsp;Gaia Castellani,&nbsp;, ,&nbsp;Giacomo Filippini,&nbsp;, ,&nbsp;Maurizio Prato,&nbsp;, ,&nbsp;Michele Melchionna*,&nbsp;, and ,&nbsp;Paolo Fornasiero*,&nbsp;","doi":"10.1021/acscatal.5c04794","DOIUrl":"10.1021/acscatal.5c04794","url":null,"abstract":"<p >The rate of scientific publications has grown exponentially over the past few decades, but this has come at the expense of reproducibility. In this context, fields like organic photocatalysis and materials synthesis have also been affected. This Perspective aims at providing general guidelines to increase trustworthiness and favor reproducibility for those interdisciplinary researchers working on organic photocatalytic transformations catalyzed by carbon-nitride-based materials. Thus, the article focuses on the importance of accurately reporting and describing all the stages of experimental work, from the photocatalyst synthesis and characterization to the evaluation of the reaction conditions, control experiments, and─more generally─all the details that may ensure reproducibility. Additionally, we investigate and discuss the risks of falling into inadequate research practices, emphasizing that irreproducibility in science is a major problem that undermines the utility and credibility of scientific research. These aspects are crucial for the scientific community, and we emphasize the need to raise awareness and educate researchers toward best experimental practices.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16792–16809"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c04794","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbon Dioxide as a Hydrogen-Transport Modulator─Disrupting Surface Hydrogen Accumulation during Propane Aromatization","authors":"Luyuan Yang,&nbsp;, ,&nbsp;Yitao Yang,&nbsp;, ,&nbsp;Min Yang,&nbsp;, ,&nbsp;Yumeng Fo,&nbsp;, ,&nbsp;Xiangyang Ji,&nbsp;, ,&nbsp;Kun Yang,&nbsp;, ,&nbsp;Guilin Liu,&nbsp;, ,&nbsp;YuHui Xia,&nbsp;, ,&nbsp;Zhen Zhao,&nbsp;, ,&nbsp;Jian Liu*,&nbsp;, and ,&nbsp;Weiyu Song*,&nbsp;","doi":"10.1021/acscatal.5c03541","DOIUrl":"10.1021/acscatal.5c03541","url":null,"abstract":"<p >Introducing CO₂ into propane (C₃H₈) aromatization presents a significant strategy for producing benzene, toluene, and xylene (BTX) while mitigating carbon emissions. This study demonstrates the dual role of CO₂ as a hydrogen-transport modulator and carbon contributor in the propane-coupled CO₂ aromatization (PCA) process. The Ga/M-Z5 catalyst, with Ga-rich outer layers for CO₂ activation and Al-rich channel intersections for aromatization, was achieved through alkali treatment of the support and subsequent chemical liquid deposition (CLD) of the active phase. This catalyst yielded a 54% CO₂ conversion and 63% BTX selectivity. The improved BTX selectivity stems from the efficient capture of hydrogen (H*) by CO₂. Mechanistic investigations, including kinetic analyses, in situ Fourier transform infrared (FTIR), mass spectrometry, and density functional theory (DFT) calculations, revealed that H* spontaneously transfers from Brønsted acid sites (BAS) to Ga–O bonds. CO₂ facilitates the extraction of H* through a pentagonal Ga–O intermediate, thereby suppressing hydrogen-induced side reactions. The high CO₂ conversion indicates that CO₂ participates in additional pathways beyond reverse water gas shift (RWGS) and reverse Boudouard reactions. Specifically, partial CO₂ interacts with oxygen-containing intermediate species, directly contributing to the reconstruction of carbon chains and the formation of aromatic products. These findings provide insights for optimizing catalyst design in PCA systems.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16771–16781"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084108","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":"Mechanistic Insights into Synergistic Enhancement of Linear α-Olefins Selectivity over Ca–Na Modified Fe5C2–ZnO Catalysts in CO Hydrogenation","authors":"Hengxuan Zhang,&nbsp;, ,&nbsp;Yan Sun*,&nbsp;, ,&nbsp;Qiwen Sun*,&nbsp;, ,&nbsp;Jiancheng Wang,&nbsp;, ,&nbsp;Zixing Shi,&nbsp;, and ,&nbsp;Junjie Liu,&nbsp;","doi":"10.1021/acscatal.5c04615","DOIUrl":"10.1021/acscatal.5c04615","url":null,"abstract":"<p >Selective synthesis of long-chain linear α-olefins (LAOs) from syngas remains a fundamental challenge due to competitive hydrogenation and water–gas shift (WGS) reactions. Herein, we report that CaO- and Na₂O-promoted Fe₅C₂–ZnO catalyst (FeZnCaNa) demonstrates prominent performance and stability in CO hydrogenation to LAOs, which achieved 97.4% of CO conversion, 73.7% of LAOs in C₄₊ olefins with LAOs space-time yield of 304.4 mg·g_cat^–1·h^–1 at 320 °C, 2.0 MPa. Comparative studies of modification with other alkaline earth metals (Mg, Sr, and Ba) underscored the unique promotional role of Ca in enhancing LAOs yield. The characterizations revealed that CaO accelerated the transformation of ZnFe₂O₄ into dispersed χ-Fe₅C₂ domains anchored at the ZnO interface. These iron carbide domains served as the principal active sites for the CO dissociation and C–C coupling. The Ca–Na–ZnO matrix modulated surface basicity, facilitating olefin desorption, and suppressing secondary hydrogenation. The ratio of olefin/paraffin attained 4.5, 58.6% of α-olefins in hydrocarbons, and suppressed CH₄ selectivity to 8.1%. In situ spectroscopic analyses further explained that CaO–Na₂O incorporation promoted CH_<i>x</i> formation, thereby accelerating chain propagation. The catalyst also exhibited a reduced CO₂ selectivity of 30.5%, attributed to the attenuated WGS activity resulting from decreased H₂O adsorption during hydrocarbon formation. This study uncovers a dual-site mechanism, offering insights for designing efficient Fe-based catalysts for viable syngas-to-olefins conversion.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16810–16826"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084110","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":"Regio- and Diastereoselective Construction of Multisubstituted C-Vinyl Glycosides via Nickel-Catalyzed Three-Component Reaction of Alkynes","authors":"Jinlin Wang,&nbsp;, ,&nbsp;Changyue Yu,&nbsp;, ,&nbsp;Qiuyu Zhong,&nbsp;, ,&nbsp;Mingjie Zeng,&nbsp;, ,&nbsp;Xiaofei He,&nbsp;, ,&nbsp;Chunpu Li,&nbsp;, ,&nbsp;Jiang Wang,&nbsp;, ,&nbsp;Wenhao Dai*,&nbsp;, and ,&nbsp;Hong Liu*,&nbsp;","doi":"10.1021/acscatal.5c03229","DOIUrl":"10.1021/acscatal.5c03229","url":null,"abstract":"<p ><i>C</i>-vinyl glycosides are important carbohydrates with various biological activities and promising applications. However, the efficient synthesis of <i>C</i>-vinyl glycosides remains challenging, typically relying on two-component couplings of glycosyl donors with olefins or alkynes. These methods often involve air-sensitive organometallic reagents, directing groups, or activating group preactivation. Notably, the construction of multisubstituted <i>C</i>-vinyl glycosides directly from alkynes remains largely underexplored in synthetic carbohydrate chemistry. Here, a convenient and efficient method for the regio- and diastereoselective synthesis of multisubstituted <i>C</i>-vinyl glycosides via a nickel-catalyzed three-component reaction involving terminal alkynes, boronic acids, and glycosyl bromides in one pot is presented. This reaction proceeds by a radical pathway and demonstrates excellent regio- and diastereoselectivity, as evidenced by the α-selective, <i>trans</i>-addition products and the addition of the glycosyl moiety installed at the terminal position of the alkyne. This method utilizes commercially available starting materials without the need for additional preactivation, features a straightforward operational procedure, and demonstrates a broad substrate scope and functional group tolerance. Furthermore, this method is suitable for the late-stage glycosylation modification of complex natural products. Overall, this approach provides a widely applicable method to synthesize multisubstituted <i>C</i>-vinyl glycosides using simple and readily available three-component starting materials in one pot.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16762–16770"},"PeriodicalIF":13.1,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084107","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}