ACS Catalysis 最新文献

{"title":"Elucidation of the Hydrogen Evolution Reaction on a Photochemical Molecular Device","authors":"Miftahussurur Hamidi Putra,&nbsp;Alexander K. Mengele,&nbsp;Benedikt Bagemihl,&nbsp;Sven Rau,&nbsp;Michael Busch,&nbsp;Axel Groß","doi":"10.1021/acscatal.6c03235","DOIUrl":"10.1021/acscatal.6c03235","url":null,"abstract":"<p>The direct conversion of solar energy to produce useful chemical products such as molecular hydrogen is one of the ultimate goals of photocatalysis. Photochemical molecular devices enable such a process cost-efficiently while offering additional benefits like repairability. We present here a full mechanism for the complete photo-induced catalytic hydrogen evolution reaction by combining a Ru-containing photocenter and a Pt-based catalytically active center in one molecular device. State-of-the-art quantum-chemical calculations shed light on the interplay between light-driven electron transfer processes and activation of protons as substrates. They reveal an induction process and the crucial role of the formation of unpaired electronic states corresponding to a doublet and subsequent higher spin multiplicities. Furthermore, the study indicates that sacrificial donors not only provide electrons but also act as a proton regulator in combination with the bridging ligand acting as a base. Based on the mechanistic understanding derived from the detailed atomistic calculations, our study provides design principles for operative photochemical molecular devices. Thus, our results that are validated through the comparison with experimental spectroscopic data are expected to alter the perspective on elementary concepts of artificial photosynthesis.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19940–19955"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050260","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":"Influence of Acidic Sites and Cu Loading on Plasma-Catalytic CO2 Hydrogenation to Methanol","authors":"Miao Miao,&nbsp;Ehsanul Hoque,&nbsp;Yaolin Wang,&nbsp;Samuel B. Portillo,&nbsp;Yuge Yao,&nbsp;Mathew Jon Rasmussen,&nbsp;Calvin Mukarakate,&nbsp;Xin Tu,&nbsp;Fanxing Li","doi":"10.1021/acscatal.6c05444","DOIUrl":"10.1021/acscatal.6c05444","url":null,"abstract":"<p>Plasma-catalytic CO₂ hydrogenation offers a promising route to methanol synthesis under near-ambient temperature and pressure by enabling nonequilibrium activation of CO₂ and H₂. However, the catalyst surface properties that govern methanol selectivity and yield under dielectric barrier discharge (DBD) plasma conditions remain insufficiently understood. Here, we investigate how support acidity and Cu functionality influence activity, selectivity, and surface reaction pathways over Cu-loaded silica–alumina catalysts. A series of silica–alumina supports containing 1–70 wt % SiO₂ were evaluated under identical DBD plasma conditions. CO₂ conversion and methanol formation exhibited a volcano-type dependence on silica content, with S30, a silica-alumina support containing 30 wt % SiO₂, giving the highest single-pass methanol yield of 8.7% among the Cu-free supports. NH₃ temperature-programmed desorption, CO₂ temperature-programmed desorption, pyridine diffuse reflectance infrared Fourier transform spectroscopy, and acidity-perturbation experiments indicate that methanol formation is not governed by total acidity or CO₂ uptake alone, but by a favorable acid environment combining predominantly Lewis acidity, relatively high medium-strength acid-site density, and low to moderate basicity. Introducing Cu increased both CO₂ conversion and methanol selectivity across the silica–alumina series, while preserving S30 as the optimal support. Under optimized conditions, S30–5Cu achieved a single-pass methanol yield of approximately 12.4% at 30 °C and near-atmospheric pressure. <em>In situ</em> plasma-coupled Fourier transform infrared spectroscopy supports a surface pathway in which adsorbed carbonate or bicarbonate species are progressively hydrogenated to formate and methoxy-like intermediates prior to methanol formation. The optimized S30–5Cu catalyst maintained relatively stable performance over 30 h and showed slightly improved performance when the reactor size was more than doubled. These results establish support acidity and Cu-acid cooperation as key design parameters for selective plasma-catalytic CO₂ hydrogenation to methanol.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20449–20462"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090608","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":"Silver-Catalyzed SiR2 Transfer Reactions via Consecutive Metal-Silylenoid and -Silylene Intermediates","authors":"Jonathan Martínez-Laguna,&nbsp;W. M. C. Sameera,&nbsp;Ana Caballero,&nbsp;Pedro J. Pérez","doi":"10.1021/acscatal.6c06046","DOIUrl":"10.1021/acscatal.6c06046","url":null,"abstract":"<p>The silver-catalyzed transfer of a SiR₂ group constitutes an underdeveloped area, mainly reduced to the work provided by the group of Woerpel. We herein expand such transformation employing silver complexes bearing trispyrazolylborate ligands that catalyze the conversion of gaseous ethylene or acetylene (as well as other olefins and alkynes) into the corresponding silacyclopropane and silacyclopropene. Mechanistic studies, supported by experimental probes and DFT calculations, allow proposing the implication of silver-silylenoid and silver-silylene species as key intermediates in a consecutive manner.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20628–20636"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092419","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 Ring-Opening Hydroboration and Enantioselective Cascade Hydroboration/Protoboration of Arylidenecyclobutanes","authors":"Xiaotang Zhou,&nbsp;Wenrui Zheng,&nbsp;Yixin Lu","doi":"10.1021/acscatal.6c06183","DOIUrl":"10.1021/acscatal.6c06183","url":null,"abstract":"<p>Arylidenecyclobutanes (ACBs) are an emerging class of five-carbon synthons for the construction of structurally complex molecules. Organoboron compounds are of central importance in modern synthetic chemistry; herein, we report copper-catalyzed ring-opening hydroboration and enantioselective cascade hydroboration/protoboration reactions that use arylidenecyclobutanes as C5 building blocks to access linear (<em>E</em>)–1,4-alkenylboronates and chiral 1,4-diboronates, respectively. Mechanistic studies and DFT calculations reveal that the CuH-catalyzed ring-opening hydroboration of ACBs proceeds through β-carbon elimination and selectively affords (<em>E</em>)–1,4-alkenylboronates. In the presence of B₂pin₂ and a proton source, this internal alkenyl intermediate can further undergo asymmetric protoboration with a Cu–Bpin species to furnish chiral 1,4-diboronate products. These boration reactions provide strategies for the ring-opening hydrofunctionalization and asymmetric 1,4-difunctionalization of ACBs. Moreover, the resulting mono- and diboronates serve as versatile intermediates for downstream transformations, enabling the efficient synthesis of bioactive molecules and chiral ligands.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20664–20674"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151380","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":"Catalytic Asymmetric Allylic Substitution with Alkynylogous Silyl Enol Ethers En Route to Chiral Allenes","authors":"Sankash Mitra,Debangshu Ghosh,Santanu Mukherjee","doi":"10.1021/acscatal.6c07098","DOIUrl":"https://doi.org/10.1021/acscatal.6c07098","url":null,"abstract":"Abstract Despite their potential as building blocks of allenes, alkynylogous enol silanes have rarely been employed in organic synthesis. Herein, we establish their utility as nucleophiles in catalytic asymmetric allylic substitution, which results in skipped enallenes bearing two vicinal stereogenic elements (axial and central chirality). This iridium-catalyzed reaction utilizes α-alkynyl silyl enol ethers as alkynylogous nucleophile for reaction with easily accessible racemic branched allylic alcohols and endows tetrasubstituted axially chiral allenones, bearing a δ-stereocenter exclusively as a single regioisomer in moderate to good diastereoselectivity (up to 11:1 dr) and in most cases with high enantioselectivity (up to &amp;gt;99.5:0.5 er). The densely functionalized γ-allylic allenones can be elaborated into useful building blocks, including a highly substituted chiral 2-allyl furan derivative. Through this work, α-alkynyl enol silanes are introduced as alkynylogous nucleophiles in transition metal catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"37 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209937","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":"Intramolecular (3 + 2) Cycloaddition of Olefins to Aromatic Aldehydes Mediated by Visible Light and a Lewis Acid Catalyst","authors":"Simone Stegbauer,&nbsp;Yi Xu,&nbsp;Erling Thyrhaug,&nbsp;Sebastian Reiter,&nbsp;Julian Zuber,&nbsp;Christian Ochsenfeld,&nbsp;Juergen Hauer,&nbsp;Thorsten Bach","doi":"10.1021/acscatal.6c06303","DOIUrl":"10.1021/acscatal.6c06303","url":null,"abstract":"<p>Benzaldehydes carrying an alkenyloxy substituent in the 3-position undergo a photocycloaddition reaction, in which the olefin adds intramolecularly to the carbonyl carbon atom and to the carbon atom C2 of the benzene core forming a cyclopentane ring. The reaction was shown to proceed upon AlBr₃ catalysis (10 mol %) by irradiation with visible light (λ = 435 nm). A total of 30 tricyclic products (44–94% yields) were obtained with high simple and facial diastereoselectivity. Transient absorption spectroscopy and mechanistic experiments suggested that both the uncatalyzed reaction at λ = 280–340 nm and the Lewis acid-catalyzed reaction occur from the triplet state.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19882–19888"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049994","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":"Bench-Stable Rh/Chiraphos Catalyzed Asymmetric Hydrogenation Reaction of Citral and Its Mechanistic Studies","authors":"Xin-Xin Wang,&nbsp;Su-Shuang Wen,&nbsp;Yuan-Hao Liu,&nbsp;Xiao-Tao Liu,&nbsp;Ming-Yao Huang,&nbsp;Shou-Fei Zhu","doi":"10.1021/acscatal.6c05113","DOIUrl":"10.1021/acscatal.6c05113","url":null,"abstract":"<p>Although the Rh/chiraphos-catalyzed asymmetric hydrogenation of citral is a main industrial route to produce important chiral fragrance monomer <span>l</span>-menthol, this process still suffers from facile deactivation, strong substrate configuration dependence, and sub-optimal enantioselectivity, which mainly attributes to the poor understanding of its mechanism. In this work, we report the synthesis of an air-stable rhodium catalyst, [Rh(chiraphos)₂]Cl, which enables over 10 recycling cycles in the asymmetric hydrogenation of citral without significant loss of activity or enantioselectivity (total turnover numbers, TONs, up to 10,000), demonstrating markedly improved stability and practical applicability. Combining experimental investigations with density functional theory (DFT) calculations, we systematically elucidate the mechanism of this asymmetric hydrogenation. The results show that the enantioselectivity and stereodependence are determined by the precise recognition of the citral head groups (CHO vs H) by the chiral cavity of the catalyst. Additionally, the chemoselectivity arises from the differences in deformation energies between the rhodium catalyst and citral caused by steric hindrance while maintaining maximum orbital overlap during the double-bond addition step. These findings offer a practical reference for the rational design of highly efficient and stereoconvergent catalytic systems for citral hydrogenation.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20372–20381"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050263","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/TEMPO-Catalyzed Direct C2-Quaternization of Pyridines with Aldehydes via Sequential N–N Bond Formation and Cleavage","authors":"Amu Wang,&nbsp;Xiaoqi Chen,&nbsp;Tong Liu,&nbsp;Meihui Liu,&nbsp;Jianwei Xu,&nbsp;Yue Zhang,&nbsp;Xiaofeng Ma","doi":"10.1021/acscatal.6c05861","DOIUrl":"10.1021/acscatal.6c05861","url":null,"abstract":"<p>Pyridine represents an indispensable class of nitrogen-containing heteroarene, yet regioselective construction of an all-carbon quaternary center at the C2 position has remained a longstanding synthetic challenge. Here, we report a Cu/TEMPO-catalyzed regioselective C2 quaternization of pyridines with readily available aldehydes via sequential formation and cleavage of N–N bonds. Specifically, the reaction involves the following: (i) N–N bond formation from pyridine and <em>O</em>-mesitylenesulfonylhydroxylamine (MSH) to the <em>N</em>-aminopyridinium (isolable or in situ), (ii) dearomatization with aldehydes via a formal [3 + 2] annulation, and (iii) Cu/TEMPO-promoted N–N bond cleavage, affording C2-quaternary products. This method efficiently delivers sterically congested C2 quaternary scaffolds with a broad substrate scope and good functional group tolerance, allowing chiral framework assembly using <em>β</em>-chiral aldehydes. Combined experimental and computational mechanistic studies elucidate a charge density-governed pathway responsible for the high C2 selectivity. Avoiding prefunctionalization of pyridine substrates, the protocol achieves chemo- and regioselective functionalization of electronically distinct pyridine motifs and late-stage modification of bioactive molecules, providing a versatile strategy for the structural diversification of azaarenes toward pharmaceutical and agrochemical applications.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20603–20615"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050267","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":"Engineering Highly Active Single-Phosphine-Coordinated Ru Catalysts for Heterogeneous N-Alkylation without Base-Additive","authors":"Sue Zhang,&nbsp;Xingju Li,&nbsp;Guifa Long,&nbsp;Lei Ma,&nbsp;Chunhui Zhang,&nbsp;Qiliang Guo,&nbsp;Ziyang Zhu,&nbsp;Miao Jiang,&nbsp;Cunyao Li,&nbsp;Li Yan,&nbsp;Yunjie Ding","doi":"10.1021/acscatal.6c05520","DOIUrl":"10.1021/acscatal.6c05520","url":null,"abstract":"<p><em>N</em>-Alkylation of amine with alcohol is an attractive route for synthesizing high-value amines. However, existing homogeneous and heterogeneous catalytic systems still suffer from limitations such as insufficient metal utilization, requirement for alkaline additives, poor recyclability, and limited intrinsic activity. Herein, we propose an alcohol-driven coordination tailoring strategy, in which the alcohol governs the transformation of pristine Ru₁-3P sites into highly active Ru₁-1P with a well-defined [RuH₂Cl₂(Ph-CHO)(PPh₃)] configuration. In base-additive-free <em>N</em>-alkylation, the Ru₁-1P/POPs catalyst delivers a TOF of 323 h^–1 and an apparent activation energy of 70.1 kJ·mol^–1, far outperforming the Ru₁-3P/POPs (145 h^–1, 103.3 kJ·mol^–1) and surpassing most reported catalysts. Comprehensive characterization confirms that Ru remains atomically dispersed even after 10 cycles. Mechanistic studies reveal that different from traditional base-dependent pathways, this catalytic cycle follows a dihydride transfer mechanism. The unique Ru₁-1P configuration significantly reduces the barrier of the rate-determining β-hydride elimination. This work provides a facile strategy for regulating single-atom coordination environments and deepens the understanding of structure-performance relationships at the molecular level.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20500–20511"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090607","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 β-Methyl Vinylation Using Allylamine as a Masked Alkenyl Electrophile","authors":"Ahyeon Cho,&nbsp;Yihan Tang,&nbsp;Jaehan Bae,&nbsp;Eun Jin Cho","doi":"10.1021/acscatal.6c06344","DOIUrl":"10.1021/acscatal.6c06344","url":null,"abstract":"<p>Direct activation of native C(sp²)–NH₂ bonds in alkenyl amines remains a largely unmet challenge in cross-coupling chemistry owing to their high bond dissociation energies, poor leaving-group ability, and competing tautomerization pathways. Herein, we report a nickel-catalyzed tandem deaminative coupling/alkene isomerization that bypasses these limitations, converting allylamine and arylboronic acids directly into (<em>E</em>)-β-methyl vinylarenes in a single base-free operation. Density Functional Theory (DFT) calculations reveal that DPEphos facilitates the key migratory insertion step, while deuterium-labeling experiments support a mechanism in which boronic acid initiates isomerization through formation of an active Ni–H species, followed by a net 1,3-hydrogen shift without requiring stoichiometric involvement of boronic acid. The method accommodates electronically diverse arylboronic acids and is readily performed on gram scale, providing a practical and stereoselective alternative to conventional olefination approaches.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20691–20699"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049993","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}