ACS Catalysis Pub Date : 2025-09-24DOI: 10.1021/acscatal.5c04859
Ramireddy Boppella, , , P. Muthu Austeria, , , Geun Ho Gu*, , and , Tae Kyu Kim*,
{"title":"Strongly Coupled Metal/Amorphous Ru/RuOx Heterostructure for Efficient Electrocatalytic Hydrogen Production","authors":"Ramireddy Boppella, , , P. Muthu Austeria, , , Geun Ho Gu*, , and , Tae Kyu Kim*, ","doi":"10.1021/acscatal.5c04859","DOIUrl":"10.1021/acscatal.5c04859","url":null,"abstract":"<p >Constructing well-defined heterostructure interfaces in catalysts is an effective strategy to break scaling relationships and accelerate reactions involving multiple intermediates. In this study, a heterostructure catalyst consisting of crystalline ruthenium (Ru) and amorphous ruthenium oxide (RuOx) nanoparticles uniformly distributed on N-doped carbon was developed by using a low-temperature (500 °C) pyrolysis method. The strong and well-defined electronic interactions at the interface between Ru and RuOx synergistically optimize hydrogen adsorption and desorption at the heterointerfaces of each particle, thereby significantly accelerating the kinetics of the hydrogen evolution reaction (HER). Consequently, the synthesized catalysts achieve pH-universal HER performance and exhibit impressively low overpotentials of 11 mV to reach a current density of 10 mA cm<sup>–2</sup> under alkaline conditions. Additionally, the anion exchange membrane electrolyzer delivers remarkably low voltages of 2.08 V to achieve a current density of 0.82 A cm<sup>–2</sup> and demonstrates prolonged stability over 100 h at a current density of 500 mA cm<sup>–2</sup>, outperforming Pt/C catalysts. Density functional theory calculations further reveal that amorphous RuOx effectively reduces the free energy barrier of the water dissociation step, while adjacent Ru promotes hydrogen evolution. This synthesis strategy offers a viable approach for the rational design and synthesis of superior HER electrocatalysts.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16981–16991"},"PeriodicalIF":13.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127982","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":"Spikes Effect: Decoding and Redesigning Pulsed Electrochemical CO2 Reduction for Enhanced C–C Coupling on Oxide-Derived Copper","authors":"Chayapat Thammaniphit, , , Jirapat Santatiwongchai, , , Sarawoot Impeng, , , Pongtanawat Khemthong, , , Kornkamon Meesombad, , , Kajornsak Faungnawakij, , , Tobias Hanrath, , , Rungthiwa Methaapanon*, , and , Pongkarn Chakthranont*, ","doi":"10.1021/acscatal.5c03544","DOIUrl":"10.1021/acscatal.5c03544","url":null,"abstract":"<p >Pulsed electrolysis has emerged as a highly effective technique for enhancing the selectivity of oxide-derived copper (OD-Cu) catalysts in the electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR), particularly toward valuable multicarbon (C<sub>2+</sub>) products. Despite extensive studies, the role of transient current spikes─brief surges in current induced by abrupt potential switching─has remained largely unexplored. In this work, we systematically dissect the contribution of these current spikes using two distinct electrolysis modes: pulsed amperometry (PA) and pulsed potentiometry (PP). By decoupling the effects of current spikes from other pulsing-induced phenomena, we demonstrate that while both methods suppress hydrogen evolution, only PA─defined by sharp, transient current spikes─substantially enhances C<sub>2+</sub> selectivity. In situ ATR-SEIRAS measurements reveal a marked increase in *CO<sub>atop</sub> intermediates under PA conditions, in line with DFT predictions that weakly bound *CO<sub>atop</sub> facilitates C–C coupling. Leveraging these mechanistic insights, we developed a double-stage pulse method that strategically amplifies current spikes and is compatible with a gas diffusion electrode (GDE) system. This method achieves a striking 9.36-fold increase in C<sub>2+</sub>/C<sub>1</sub> selectivity at an industrially relevant current density of 450 mA cm<sup>–2</sup>. Our findings uncover a previously overlooked yet critical parameter in pulsed electrolysis, and by leveraging this insight, we establish a powerful and scalable method to significantly enhance CO<sub>2</sub>-to-C<sub>2+</sub> conversion for practical applications.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"17003–17014"},"PeriodicalIF":13.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c03544","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134121","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":"Tuning Protonation Microenvironments via Edge-Linker Design in One-Dimensional Imine-Linked Covalent Organic Frameworks for Enhanced Photocatalytic Hydrogen Evolution","authors":"Pan-Ke Zhou, , , Caihong Liang, , , Cong Zhang, , , Yuxing Huang, , , Ziyue Yu, , , Chao Lin, , , Chao Zhang, , , Qiqi Sun, , , Yupeng Song, , , Xiao-Rui Ren, , , Sibo Wang, , , Dong Wang, , , Yeng Ming Lam, , and , Xiong Chen*, ","doi":"10.1021/acscatal.5c05316","DOIUrl":"10.1021/acscatal.5c05316","url":null,"abstract":"<p >Protonated covalent organic frameworks (COFs) have attracted considerable attention as promising photocatalysts for hydrogen evolution. Despite significant progress, prior investigations have predominantly targeted protonation at imine linkages, overlooking the broader influence of other structural motifs on the photocatalytic performance. Herein, we propose an “edge-linker engineering” strategy to tune the protonation microenvironment and electronic structure of one-dimensional (1D) imine-linked COFs by incorporating distinct edge linkers: −CH<sub>2</sub>–, −O–, and −S–, yielding COF-MDA, COF-ODA, and COF-SDA, respectively. While protonation primarily occurs at imine bonds, the nature of the edge linker profoundly influences the electronic structure of the framework. Notably, the sulfur-containing a −S– linker in COF-SDA significantly enhances charge delocalization and facilitates the hydrogen reduction process. As a result, COF-SDA exhibits the highest hydrogen evolution rate under visible-light irradiation, using ascorbic acid as the protonation reagent, outperforming its analogs. Density functional theory calculations elucidate that the COF-SDA exhibits enhanced hydrogen binding affinity and a reduced energy for proton reduction, highlighting the critical role of edge-linker-mediated electronic modulation. This study establishes a comprehensive structure–function relationship among edge-site design, protonation behavior, and photocatalytic activity in 1D COFs, providing a molecular design paradigm for developing polymer photocatalysts for solar-to-hydrogen conversion.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16992–17002"},"PeriodicalIF":13.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133463","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}
ACS Catalysis Pub Date : 2025-09-23DOI: 10.1021/acscatal.5c02778
Tobia Casadei, , , Alberto Piccoli, , , Davide Zeppilli, , , Laura Orian, , , Abdirisak A. Isse, , and , Marco Fantin*,
{"title":"Rapid Electrochemical Assessment of Excited-State Quenching Dynamics","authors":"Tobia Casadei, , , Alberto Piccoli, , , Davide Zeppilli, , , Laura Orian, , , Abdirisak A. Isse, , and , Marco Fantin*, ","doi":"10.1021/acscatal.5c02778","DOIUrl":"10.1021/acscatal.5c02778","url":null,"abstract":"<p >Recent advancements in electro-photoredox catalysis (e-PRC) and consecutive photoinduced electron transfer (conPET) have pushed the energy limits of conventional photocatalysis. Both methods produce open-shell intermediate catalysts that, upon light absorption, become highly reducing or oxidizing, enabling challenging reactions. Despite their widespread use, the mechanisms of e-PRC and conPET reactions remain debated, in part due to a lack of quantitative data in most studies─particularly single-electron transfer rate constants (<i>k</i><sub>SET</sub>) between excited-state catalysts and substrates. We present a straightforward electrochemical method for determining <i>k</i><sub>SET</sub> using cyclic voltammetry (CV) under light irradiation, paired with electrochemical simulation. Using inexpensive LEDs and standard potentiostats, we investigated the reactivity of excited-state anions of a perylene diimide dye (PDI), the seminal catalyst of conPET reactions. CV was used to study the photochemical reactivity of both reduced species of PDI, *PDI<sup>•–</sup> and *PDI<sup>2–</sup>, in the reductive cleavage of carbon–halogen bonds in alkyl and aryl halides. The extreme reactivity of these excited-state anions is confirmed, with quenching rate constants of 10<sup>7</sup> and 10<sup>10</sup> M<sup>–1</sup> s<sup>–1</sup> for *PDI<sup>•–</sup> and *PDI<sup>2–</sup>, respectively, consistent with theoretical and experimental data. The voltammetric approach presented here provides a rapid and reliable tool for studying the excited-state reactivity of labile intermediates utilized in e-PRC and conPET systems, including both radical anions and dianions.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16938–16952"},"PeriodicalIF":13.1,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c02778","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127983","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}
ACS Catalysis Pub Date : 2025-09-23DOI: 10.1021/acscatal.5c05469
Mahmoud R. Saleh, , , Mahmoud Afrasi, , , Ajay H. Bansode, , , Poulami Ghosh, , , Dan E. Wise, , and , Marvin Parasram*,
{"title":"Photochromic Oxime Directing Groups for Spatially Controlled Pd-Catalyzed C–H Difunctionalization with Tandem Electrophiles","authors":"Mahmoud R. Saleh, , , Mahmoud Afrasi, , , Ajay H. Bansode, , , Poulami Ghosh, , , Dan E. Wise, , and , Marvin Parasram*, ","doi":"10.1021/acscatal.5c05469","DOIUrl":"10.1021/acscatal.5c05469","url":null,"abstract":"<p >Herein, we report the employment of oxime ethers as photochromic directing groups for the controlled functionalization of spatially and inherently distinct C(sp<sup>2</sup>)–H/C(sp<sup>3</sup>)–H bonds. Our approach features a semi-two-pot protocol for Pd-catalyzed C(sp<sup>2</sup>)–H oxygenation, photoisomerization, and Pd-catalyzed C(sp<sup>3</sup>)–H arylation for the synthesis of difunctionalized oxime derivatives in a highly selective and controlled manner. Notably, we illustrate the rare utilization of hypervalent iodine reagents as tandem electrophiles for C–H difunctionalization. The reverse sequence of functionalization events can be achieved thermally, thereby providing a platform for full directing group-controlled C–H difunctionalization. Overall, this work highlights that photochromic directing groups can provide an avenue for positionally controlled C–H difunctionalization.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16917–16923"},"PeriodicalIF":13.1,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c05469","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116719","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}
ACS Catalysis Pub Date : 2025-09-23DOI: 10.1021/acscatal.5c04494
Zachary M. Gdowski, , , Rishi Raj, , , Aditya Bhan, , , K. Andre Mkhoyan, , , Mahesh K. Mahanthappa*, , and , Frank S. Bates*,
{"title":"Polymer Upcycling by Catalytic Hydrogenolysis: The Role of Polyolefin Short-Chain Branching","authors":"Zachary M. Gdowski, , , Rishi Raj, , , Aditya Bhan, , , K. Andre Mkhoyan, , , Mahesh K. Mahanthappa*, , and , Frank S. Bates*, ","doi":"10.1021/acscatal.5c04494","DOIUrl":"10.1021/acscatal.5c04494","url":null,"abstract":"<p >We report the hydrogenolysis of model short-chain branched polyolefins over a heterogeneous catalyst comprising 5–10 nm diameter Pt–Re nanoparticles supported on macroporous SiO<sub>2</sub> (0.1–1 μm pore diameters) to assess how polymer chain microstructure affects reactivity for upcycling applications. Living anionic homopolymerizations of 1,3-butadiene, isoprene, and styrene sometimes with a polar modifier followed by surface-catalyzed saturation afforded a series of narrow dispersity polyolefins with well-defined number-average molecular weights (<i>M</i><sub>n</sub>) and variable branch types and contents, including poly(ethylene-<i>co</i>-1-butene) copolymers (denoted hPB) with 1.5–38 ethyl branches per 100 backbone carbons, poly(ethylene-<i>alt</i>-propylene) (PEP), and poly(cyclohexylethylene) (PCHE). A model high-density polyethylene (HDPE) of comparable <i>M</i><sub>n</sub> with no short chain branches was also produced by tandem ring-opening metathesis polymerization and catalytic hydrogenation. Size-exclusion chromatography (SEC) analyses of the products of polymer hydrogenolysis in cyclohexane at <i>T</i> = 140–200 °C for ≤17 h over the Pt–Re/SiO<sub>2</sub> catalyst show that the amount of short chain branching impacts the extent of polymer cleavage. Specifically, <i>M</i><sub>n</sub> reductions of nearly 100-fold are achieved for HDPE and lightly branched hPB (1.5–10 branches per 100 backbone carbon atoms), 10-fold for PEP, and less than 2-fold for the highly branched hPB and PCHE. These strong correlations between branching and susceptibility to hydrogenolysis in polyolefins have important implications for the ability to upcycle waste single-use hydrocarbon polymers and their mixtures.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16924–16937"},"PeriodicalIF":13.1,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116718","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}
ACS Catalysis Pub Date : 2025-09-23DOI: 10.1021/acscatal.5c03831
Bo Tang*, , , Xu Zuo, , , Ang Li, , , Jiajun Wang, , , Haojun Zou, , , Lili Xu, , and , Weili Dai*,
{"title":"Lewis Acidic Zeolite-Encapsulated Bimetallic Au–Pt Nanoparticles as Robust Catalysts for the Conversion of Glycerol to Methyl Lactate","authors":"Bo Tang*, , , Xu Zuo, , , Ang Li, , , Jiajun Wang, , , Haojun Zou, , , Lili Xu, , and , Weili Dai*, ","doi":"10.1021/acscatal.5c03831","DOIUrl":"10.1021/acscatal.5c03831","url":null,"abstract":"<p >Alkyl lactates can be produced via a glycerol oxidation-rearrangement route, which is a promising alternative to the microbial fermentation-based technology but is still hindered by the lack of an efficient catalyst. Herein, we reported the successful fabrication of well-defined bimetallic Au–Pt nanoparticles confined inside the Snβ zeolite, i.e., Au<sub><i>x</i></sub>Pt<sub><i>y</i></sub>@Snβ, using a mercaptosilane-assisted structure reconstruction strategy. Owing to the synergistic effect of bimetallic Au–Pt species and the unique Lewis acidic framework Sn, the optimized Au<sub>1</sub>Pt<sub>3</sub>@Snβ demonstrated superior catalytic performance in the conversion of glycerol to methyl lactate, achieving a 78.8% methyl lactate yield and a TOF of 335 h<sup>–1</sup> at 413 K and 0.5 MPa air, which surpasses most previously reported heterogeneous catalysts under similar reaction conditions. The confinement environment of zeolite can not only provide spatial restriction but also induce a strong interaction between encapsulated Au–Pt nanoparticles and framework Sn, thus inhibiting metal sintering and leaching during catalysis. Experimental and theoretical calculations (DFT) results explicated the critical role of bimetallic Au–Pt synergy in activating O<sub>2</sub> and facilitating a lower energy barrier for glycerol dehydrogenation, thereby promoting the catalytic performance.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16953–16967"},"PeriodicalIF":13.1,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127984","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":"Single-Atom Iridium Orchestrates a Reaction Pathway Shift to Activate Lattice Oxygen for Efficient Oxygen Evolution","authors":"Zhongxin Duan, , , Zhenduo Cui, , , Zhonghui Gao*, , , Wence Xu, , , Yanqin Liang, , , Hui Jiang, , , Zhaoyang Li, , , Fang Wang*, , and , Shengli Zhu*, ","doi":"10.1021/acscatal.5c05674","DOIUrl":"10.1021/acscatal.5c05674","url":null,"abstract":"<p >Overcoming the intrinsic limitations of the oxygen evolution reaction (OER) remains a formidable challenge in the pursuit of efficient water splitting. Herein, we demonstrate a method for selective anchoring of an iridium atom near a NiFe layered double hydroxide iron site. This strategy enables the direct formation of the O–O coupling pathway via the lattice oxygen mechanism (LOM), thus circumventing the thermodynamic constraints imposed by the conventional adsorbate evolution mechanism (AEM). The catalyst achieves an ultralow overpotential of 213 mV at 50 mA cm<sup>–2</sup> and maintains 1000 h of operation at 100 mA cm<sup>–2</sup> in alkaline media. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), in situ electrochemical Raman spectroscopy, TMA<sup>+</sup> cation probing, and pH-dependent analysis collectively provide compelling evidence for the lattice oxygen mechanism (LOM) pathway. When integrated into an anion exchange membrane water electrolyzer (AEMWE), the system delivers 1 A cm<sup>–2</sup> at <1.73 V. Furthermore, density functional theory (DFT) calculations and X-ray absorption fine structure analysis (XAFS) demonstrate that the Ir single atoms enhance metal–oxygen hybridization and raise the O 2p band center, thus promoting the electronic transition from AEM to LOM. These findings not only advance our understanding of single-atom-modulated catalysts but also highlight their potential in optimizing OER systems for energy applications.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16882–16892"},"PeriodicalIF":13.1,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116721","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}
ACS Catalysis Pub Date : 2025-09-22DOI: 10.1021/acscatal.5c04650
Tyler A. Alsup, , , Diana P. Łomowska-Keehner, , , Melvin Osei Opoku, , , Zining Li, , , Caitlin A. McCadden, , , Tracy Qu, , , Glen Gillia, , , Jordan Nafie, , and , Jeffrey D. Rudolf*,
{"title":"Discovery of UbiA-Type Cyathane Synthases in Bacteria","authors":"Tyler A. Alsup, , , Diana P. Łomowska-Keehner, , , Melvin Osei Opoku, , , Zining Li, , , Caitlin A. McCadden, , , Tracy Qu, , , Glen Gillia, , , Jordan Nafie, , and , Jeffrey D. Rudolf*, ","doi":"10.1021/acscatal.5c04650","DOIUrl":"10.1021/acscatal.5c04650","url":null,"abstract":"<p >UbiA-type terpene synthases, traditionally annotated as prenyltransferases, have been shown to catalyze terpene cyclization in recent years, expanding their catalytic repertoire beyond primary metabolism. Here, we report on the genome-guided discovery and functional characterization of bacterial UbiA diterpene synthases (diTSs). Using a geranylgeranyl diphosphate (GGPP)-overproducing <i>Escherichia coli</i> system, we screened 32 candidate enzymes and identified five that generate structurally diverse diterpenes, two of which represent bacterial examples of cyathane synthases. Site-directed mutagenesis uncovered active-site residues that influence product formation, directing cyclization toward mono- or tricyclic products. This study expands the known catalytic repertoire of UbiA enzymes and highlights their untapped potential in bacterial terpenoid biosynthesis. Our findings suggest that bacteria may produce diverse and bioactive diterpenoids using UbiA TSs for the first committed biosynthetic step, warranting further exploration of UbiA TSs for natural product discovery.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16873–16881"},"PeriodicalIF":13.1,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103882","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}
ACS Catalysis Pub Date : 2025-09-22DOI: 10.1021/acscatal.5c05099
Sydney E. Towell, , , Fu-Sheng Wang, , , Daniel R. Godfrey, , and , Aleksandr V. Zhukhovitskiy*,
{"title":"Mechanistic Insights toward Accelerated Selenium-Catalyzed Allylic and Propargylic C–H Amination","authors":"Sydney E. Towell, , , Fu-Sheng Wang, , , Daniel R. Godfrey, , and , Aleksandr V. Zhukhovitskiy*, ","doi":"10.1021/acscatal.5c05099","DOIUrl":"10.1021/acscatal.5c05099","url":null,"abstract":"<p >Catalytic allylic and propargylic C–H aminations present valuable opportunities for the late-stage modification of pharmacophores in drug discovery. However, modern methodology is limited by reliance on expensive transition metal catalysts or slow reactivity. While selenium-catalyzed methods avoid some of these issues, in their current state, they require high catalyst loadings (15 mol %), superstoichiometric quantities of the amine and oxidant source, and long reaction times. Furthermore, our understanding of the mechanism remains incomplete: e.g., what is the catalytically active species, how is the precatalyst converted to it, and what is the role of the ligand? In this paper, we report an <i>N</i>-heterocyclic carbene selenide (NHC-Se) that allows for substantially reduced loadings of selenium without sacrificing reaction time, improves conversions and yields for challenging substrates, and even exhibits the capacity to catalyze 1,4-allylic diamination of alkenes. To understand the origin of the enhanced activity compared to the state-of-the-art NHC-Se precatalyst, we conducted a mechanistic study that supports ligand-free selenium diimide as the active enophile in these systems, while the NHC-derived byproducts, like the corresponding urea, facilitate turnover. We also isolate and structurally characterize NHC-Se mono- and diimido species and explore their mechanistic role. Thus, this work advances C–H amination methodology, our understanding of its mechanistic underpinnings, and selenium chemistry at large.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 19","pages":"16908–16916"},"PeriodicalIF":13.1,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116720","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}
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