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Machine Learning-Guided Discovery of Robust Conditions for Photochemical Nickel-Catalyzed Cysteine Arylation 机器学习引导下发现光化学镍催化半胱氨酸芳基化的稳健条件
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-26 DOI: 10.1021/acscatal.6c06459
Nikolaos Kaplaneris, Elia Savino, Zhen He, Naya A. Stini, Michael Vanzella, Méritxell Fillols, Petros Siasiaridis, Oliver Bayley, Kim S. Halskov, Wouter F. J. Hogendorf, Felix Wojcik, Christoforos G. Kokotos, Timothy Noël
{"title":"Machine Learning-Guided Discovery of Robust Conditions for Photochemical Nickel-Catalyzed Cysteine Arylation","authors":"Nikolaos Kaplaneris,&nbsp;Elia Savino,&nbsp;Zhen He,&nbsp;Naya A. Stini,&nbsp;Michael Vanzella,&nbsp;Méritxell Fillols,&nbsp;Petros Siasiaridis,&nbsp;Oliver Bayley,&nbsp;Kim S. Halskov,&nbsp;Wouter F. J. Hogendorf,&nbsp;Felix Wojcik,&nbsp;Christoforos G. Kokotos,&nbsp;Timothy Noël","doi":"10.1021/acscatal.6c06459","DOIUrl":"10.1021/acscatal.6c06459","url":null,"abstract":"<p>Late-stage functionalization (LSF) of peptides offers direct access to structurally diverse analogues, but developing general, chemoselective protocols remains challenging due to the complexity of peptide substrates and the vast number of reaction variables. Traditional optimization methods are slow and resource-intensive, limiting the exploration of emerging chemistries. Here, we present a machine learning (ML)-guided workflow that rapidly identifies robust and scalable conditions for the nickel-catalyzed photochemical arylation of cysteine residues. Using arylthianthrenium salts as versatile electrophiles and graphitic carbon nitride as a reusable photocatalyst, we implemented a two-stage active learning strategy: initially, an embedding-based model to efficiently narrow the categorical space, followed by Bayesian optimization of continuous parameters. Importantly, this ML-guided workflow pairs seamlessly with conventional laboratory practices, eliminating the need for specialized high-throughput experimentation (HTE) equipment such as microtiter plates. This approach enabled the discovery of high-yielding, chemist-friendly conditions with minimal experimental cost. The resulting protocol shows high site- and chemoselectivity across diverse peptides, saccharides, and the (hetero)arylthianthrenium coupling partners and can be scaled to gram quantities while allowing photocatalyst recycling. More broadly, this work demonstrates how data-driven optimization can accelerate the development of general LSF methodologies, providing a transferable strategy for modern reaction discovery.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20723–20735"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050261","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}
引用次数: 0
Tightly Coupled FeNi Alloy/NiO Interface Derived from an LDH Precursor Promotes Deep Hydrodeoxygenation of p-Cresol 由LDH前驱体衍生的FeNi合金/NiO紧密耦合界面促进了对甲酚的深度加氢脱氧
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-26 DOI: 10.1021/acscatal.6c06421
Guosong Wang, Dong Zhang, Yihui Song, Haitao Meng, Dan Li, Chong Peng
{"title":"Tightly Coupled FeNi Alloy/NiO Interface Derived from an LDH Precursor Promotes Deep Hydrodeoxygenation of p-Cresol","authors":"Guosong Wang,&nbsp;Dong Zhang,&nbsp;Yihui Song,&nbsp;Haitao Meng,&nbsp;Dan Li,&nbsp;Chong Peng","doi":"10.1021/acscatal.6c06421","DOIUrl":"10.1021/acscatal.6c06421","url":null,"abstract":"<p>Hydrodeoxygenation (HDO) of lignin derivatives is a promising strategy for biomass utilization, but its catalytic performance is often unsatisfactory for non-noble metal catalysts. This hinders the industrialization process of biomass utilization. Herein, we obtained a FeNi-Cop catalyst with a tightly coupled interface between FeNi alloy and NiO by a hydrotalcite-derived strategy. The effect of this interface on the <em>p</em>-cresol HDO was studied by XRD, HRTEM, H<sub>2</sub>-TPR, NH<sub>3</sub>-TPD, XPS, in situ FTIR, and DFT calculations. FeNi-Cop catalyst facilitates hydrogen activation and can promote the dehydration reaction of methylcyclohexanol, a key intermediate, through the electronic regulation of the interface and acid sites. High space-time yield (STY) of methylcyclohexane was obtained, and good catalytic performance could be maintained after 10 cycles. This tightly coupled alloy/oxide interface provides a feasible approach for the design of non-noble metal catalysts.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20712–20722"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050266","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}
引用次数: 0
Oxygen Management in Ruthenium–Cerium Anode Facilitates Water Adsorption and Bubble Desorption for Oxygen Evolution at High Current Densities 钌铈阳极的氧管理促进了高电流密度下析氧的水吸附和气泡脱附
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-26 DOI: 10.1021/acscatal.6c04063
Aparna M. Das, Viktoria Golovanova, Anku Guha, Bruna Ferreira Gomes, David Llorens Rauret, Alba Garzón Manjón, Adrián Pinilla-Sanchez, Lulu Li, Jordi Morales-Vidal, Tengyu Chen, Lu Xia, Ranit Ram, Andrea Rogolino, Carlos M. S. Lobo, Kaiwen Wang, Teresa Andreu, Christina Roth, Juan Jesús Velasco-Vélez, Jordi Arbiol, Núria López, F. Pelayo García de Arquer
{"title":"Oxygen Management in Ruthenium–Cerium Anode Facilitates Water Adsorption and Bubble Desorption for Oxygen Evolution at High Current Densities","authors":"Aparna M. Das,&nbsp;Viktoria Golovanova,&nbsp;Anku Guha,&nbsp;Bruna Ferreira Gomes,&nbsp;David Llorens Rauret,&nbsp;Alba Garzón Manjón,&nbsp;Adrián Pinilla-Sanchez,&nbsp;Lulu Li,&nbsp;Jordi Morales-Vidal,&nbsp;Tengyu Chen,&nbsp;Lu Xia,&nbsp;Ranit Ram,&nbsp;Andrea Rogolino,&nbsp;Carlos M. S. Lobo,&nbsp;Kaiwen Wang,&nbsp;Teresa Andreu,&nbsp;Christina Roth,&nbsp;Juan Jesús Velasco-Vélez,&nbsp;Jordi Arbiol,&nbsp;Núria López,&nbsp;F. Pelayo García de Arquer","doi":"10.1021/acscatal.6c04063","DOIUrl":"10.1021/acscatal.6c04063","url":null,"abstract":"<p>The production of hydrogen via acidic water electrolysis requires efficient oxygen evolution reaction (OER) at high current densities. However, this is often limited by oxygen bubble accumulation, which blocks active sites and restricts water access. Although bubble release and water access are closely linked, these interfacial processes are rarely controlled together. We engineer a ruthenium oxide–cerium oxide (RuO<sub>x</sub>–CeO<sub>x</sub>) catalyst where CeO<sub>x</sub> is observed to modulate surface oxygen vacancies during operation, enhancing water availability and promoting bubble detachment in RuO<sub>x</sub>. <em>In situ</em> X-ray absorption studies show that CeO<sub>x</sub> dynamically facilitates the formation of surface oxygen vacancies, and Raman spectroscopy indicates improved electrolyte wetting under applied potentials. Simulations reveal that oxygen-depleted RuO<sub>x</sub> surfaces favor water accumulation, thereby facilitating the initiation of OER. This results in distinct bubble dynamics with a four-fold reduction in median bubble contact area and lower overpotentials at high current densities in RuO<sub>x</sub>–CeO<sub>x</sub> compared to RuO<sub>x</sub>. Implementation in a proton exchange membrane water electrolyzer achieves a 0.1 V reduction in full-cell potential at 1 A·cm<sup>–2</sup>, linking surface chemistry to device-level outcomes.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20038–20051"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050269","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}
引用次数: 0
Engineering In/In2O3 Heterointerfaces for Highly Efficient Acidic CO2-to-HCOOH Electroreduction at Ampere-Level Current Density 工程In/In2O3异质界面在安培电流密度下的高效酸性co2 - hcooh电还原
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-29 DOI: 10.1021/acscatal.6c05578
Tingting Fan, Lei Wang, Hui-Lei Ma, Yuqi Zhang, Jiguang Zhang, Yuhan Wu, Lei Yuan, Wenrui Wan, Xiaodong Yi, Xia-Guang Zhang, Ning Yan, Jianji Wang
{"title":"Engineering In/In2O3 Heterointerfaces for Highly Efficient Acidic CO2-to-HCOOH Electroreduction at Ampere-Level Current Density","authors":"Tingting Fan,&nbsp;Lei Wang,&nbsp;Hui-Lei Ma,&nbsp;Yuqi Zhang,&nbsp;Jiguang Zhang,&nbsp;Yuhan Wu,&nbsp;Lei Yuan,&nbsp;Wenrui Wan,&nbsp;Xiaodong Yi,&nbsp;Xia-Guang Zhang,&nbsp;Ning Yan,&nbsp;Jianji Wang","doi":"10.1021/acscatal.6c05578","DOIUrl":"10.1021/acscatal.6c05578","url":null,"abstract":"<p>Efficient acidic CO<sub>2</sub> electroreduction to formic acid (HCOOH) offers a promising pathway for chemical manufacturing, yet catalyst stability remains a major obstacle. For example, while In<sub>2</sub>O<sub>3</sub> catalysts exhibit high selectivity toward HCOOH, the cationic In<sup>3+</sup> species are prone to reduction to metallic In under harsh acidic conditions. Herein, we demonstrate that high-valent In<sup>3+</sup> species are dynamically regenerated by integrating In/In<sub>2</sub>O<sub>3</sub> heterointerfaces with periodic anodic pulses, preventing the irreversible deactivation observed under conventional steady-state conditions. Combined in situ characterizations and theoretical calculations reveal that the heterointerface enhances *OCHO intermediate formation and accelerates interfacial water dissociation to supply abundant *H, enabling highly efficient and stable HCOOH production. As a result, the In/In<sub>2</sub>O<sub>3</sub> catalyst achieves a HCOOH Faradaic efficiency of 95.5% at –1.0 A cm<sup>–2</sup> and maintains stability for 133 h under pulsed electrolysis in pH 2 electrolyte, significantly outperforming the neat In catalyst. Moreover, concentrated HCOOH (1.43 M) is directly produced at –0.4 A cm<sup>–2</sup> in a solid-state electrolyte reactor. This work demonstrates that metastable high-valent active sites can be sustained under industrially relevant acidic CO<sub>2</sub> electrolysis through synergistic interfacial stabilization and dynamic electrochemical regeneration, providing a universal strategy for catalyst-state management in electrochemical systems.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20541–20550"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090606","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}
引用次数: 0
Modular Synthesis of γ-Chloro Ketones through Carbochlorination of Alkenes Mediated by Copper(I) Photoredox Catalysis 铜光氧化还原催化烯烃碳氯化合成γ-氯酮的模块化研究
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-06 DOI: 10.1021/acscatal.6c06764
Finn Hagen, Sabrina L. Simmet, Hanno Stuntebeck, Kevin T. A. Dang, Tobias Morack
{"title":"Modular Synthesis of γ-Chloro Ketones through Carbochlorination of Alkenes Mediated by Copper(I) Photoredox Catalysis","authors":"Finn Hagen,&nbsp;Sabrina L. Simmet,&nbsp;Hanno Stuntebeck,&nbsp;Kevin T. A. Dang,&nbsp;Tobias Morack","doi":"10.1021/acscatal.6c06764","DOIUrl":"10.1021/acscatal.6c06764","url":null,"abstract":"<p>γ-Chloro ketones are multifunctional synthons that serve as versatile linchpins for the rapid assembly of molecular complexity. Despite this strategic value, their broader adoption remains conspicuously limited as a consequence of the intrinsic challenges associated with their preparation. Herein, we report a visible-light-driven, copper-catalyzed carbochlorination of alkenes that provides γ-chloro ketones from readily available α-chloro analogues. The resulting products engage as versatile building blocks, enabling direct access to a range of heterocycles, (spiro-)cyclopropanes, and γ-functionalized ketones. A key feature of this transformation is the use of heteroleptic Cu(I) photocatalysts, which combine strong reducing power in the excited state with ligand exchange processes that enable terminal bond formation at the copper center. This duality enables reactivity that is not readily accessed with common organic or iridium-based photocatalysts. Mechanistic studies support the involvement of two active photocatalytic species that together enable the challenging access to α-keto radicals from α-chloro ketones. They further underscore the role of the dmp ligand in stabilizing Cu(II) intermediates, thereby facilitating carbon−chlorine bond formation. This simple and efficient methodology provides expedient access to multifunctional building blocks, set up for downstream diversification.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20780–20790"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092017","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}
引用次数: 0
Spatial Proximity and Charge Transfer: Two Key Factors Governing Brønsted/Lewis Acid Synergy in Dealuminated H-ZSM-5 Zeolites 空间接近和电荷转移:影响H-ZSM-5脱铝沸石中Brønsted/Lewis酸协同作用的两个关键因素
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-07 DOI: 10.1021/acscatal.6c05379
Yueying Chu, Zhigao Li, Yujie Xi, Chao Wang, Guodong Qi, Jun Xu, Feng Deng
{"title":"Spatial Proximity and Charge Transfer: Two Key Factors Governing Brønsted/Lewis Acid Synergy in Dealuminated H-ZSM-5 Zeolites","authors":"Yueying Chu,&nbsp;Zhigao Li,&nbsp;Yujie Xi,&nbsp;Chao Wang,&nbsp;Guodong Qi,&nbsp;Jun Xu,&nbsp;Feng Deng","doi":"10.1021/acscatal.6c05379","DOIUrl":"10.1021/acscatal.6c05379","url":null,"abstract":"<p>In dealuminated zeolites, extra-framework Al (EFAL) species released from the zeolite framework can act as Lewis acid sites (LAS) and exhibit a synergistic effect with neighboring Brønsted acid sites (BAS). However, the factors governing this synergy remain elusive. In this study, we elucidate how BAS and EFAL species cooperatively modulate the acidity of dealuminated H-ZSM-5 zeolites and then extend this understanding to the activation of propane. Through a combination of high-level density functional theory calculations, including ab initio thermodynamics (AITD) and ab initio molecular dynamics (AIMD), the charge transfer of EFAL species and their spatial proximity to BAS are identified as two key factors governing both zeolite acid strength and catalytic performance. The results indicate that a BAS–EFAL distance less than 4.5 Å plays a crucial role in enhancing BAS acidity, owing to strong electrostatic interactions. Within this proximity, the extent of charge transfer from cationic EFAL to the zeolite framework significantly increases the intrinsic acid strength of BAS. The presence of trace water slightly reduces the acid strength but preserves the increased acidity of BAS/EFAL pairs compared to isolated BAS. AITD confirms the stability of hydrated BAS/EFAL species under operando conditions, while AIMD reveals that active complexes adopt either penta-coordinated (e.g., BAS/[Al(H<sub>2</sub>O)]<sup>3+</sup> and BAS/Al<sup>3+</sup>) or tetra-coordinated (e.g., BAS/[Al(OH)(H<sub>2</sub>O)]<sup>2+</sup> and BAS/[Al(OH)<sub>2</sub>]<sup>+</sup>) configurations, with EFAL autonomically adjusting its coordination to framework oxygens. We further evaluate the catalytic activity of BAS/EFAL sites in propane cracking and dehydrogenation and find that cationic EFAL species significantly lower the activation enthalpy, thereby improving the reaction activity. This work demonstrates that the charge transfer from EFAL species to the framework and the BAS–EFAL distance could serve as design principles for the rational development of highly efficient zeolite catalysts.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20437–20448"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092422","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}
引用次数: 0
Multimodal Synergy via Interfacial Charge Regulation Boosts Solar-Driven Photothermal CO2 Splitting in Perovskite-Ceria Composites 通过界面电荷调节的多模态协同作用促进钙钛矿-铈复合材料中太阳能驱动的光热CO2分裂
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-01 DOI: 10.1021/acscatal.6c07088
Qi Wang, Yimin Xuan, Ke Gao, Liang Teng, Longzhen Zhang, Jin Wang, Xianglei Liu
{"title":"Multimodal Synergy via Interfacial Charge Regulation Boosts Solar-Driven Photothermal CO2 Splitting in Perovskite-Ceria Composites","authors":"Qi Wang,&nbsp;Yimin Xuan,&nbsp;Ke Gao,&nbsp;Liang Teng,&nbsp;Longzhen Zhang,&nbsp;Jin Wang,&nbsp;Xianglei Liu","doi":"10.1021/acscatal.6c07088","DOIUrl":"10.1021/acscatal.6c07088","url":null,"abstract":"<p>Solar-driven thermochemical CO<sub>2</sub> splitting is a scalable and promising approach for establishing a carbon-neutral energy system. However, its extremely high conversion temperatures greatly limit its energy efficiency and widespread application. This extreme temperature requirement is fundamentally dictated by the thermodynamic bottleneck of lattice-oxygen activation. Here, we propose an interfacial charge regulation strategy that couples photogenerated carriers with thermochemical lattice-oxygen redox within a heterostructured perovskite-ceria composite. This design creates multimodal synergy among light-driven charge generation, interfacial charge regulation, and thermally activated lattice-oxygen redox. For the designed CaMn<sub>0.875</sub>Ti<sub>0.125</sub>O<sub>3</sub>/CeO<sub>2</sub> composite, <em>in situ</em> characterizations and theoretical calculations reveal that charge redistribution facilitates the electronic population of metal−oxygen antibonding states. This targeted electronic population weakens specific metal−oxygen bonds, modulating the local oxygen vacancy formation energy and promoting highly reactive CO<sub>2</sub><sup><strong>·</strong>−</sup> radical anion formation. Consistent with this field-driven interfacial regulation, the composite delivers a CO yield of 1017.48 μmol g<sup>−1</sup> at a substantially lowered operating temperature of 860 °C, a 300-fold enhancement over the purely thermal baseline. Ultimately, this work moves beyond conventional charge-separation models by identifying rational interfacial field engineering as an electronic strategy to modulate local defect thermodynamics for high-efficiency CO<sub>2</sub>-to-fuel conversion.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20809–20821"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090602","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}
引用次数: 0
Chiral 3,4-H2-Dihydro-Monothiobinaphthol-Derived Bifunctional Catalysts: Design, Synthesis, and Application to Enantioselective Disulfuration of Aza[5]Helicenes 手性3,4- h2 -二氢单硫代萘酚衍生双功能催化剂:设计、合成及在Aza b[5]螺旋烯对映选择性二硫化反应中的应用
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-05 DOI: 10.1021/acscatal.6c06318
Ze-Long Li, Qing-Yun Cai, Yu-Xuan Huo, Xue-Qing Gong, Hui-Yun Luo, Zhi-Min Chen
{"title":"Chiral 3,4-H2-Dihydro-Monothiobinaphthol-Derived Bifunctional Catalysts: Design, Synthesis, and Application to Enantioselective Disulfuration of Aza[5]Helicenes","authors":"Ze-Long Li,&nbsp;Qing-Yun Cai,&nbsp;Yu-Xuan Huo,&nbsp;Xue-Qing Gong,&nbsp;Hui-Yun Luo,&nbsp;Zhi-Min Chen","doi":"10.1021/acscatal.6c06318","DOIUrl":"10.1021/acscatal.6c06318","url":null,"abstract":"<p>We herein report the design and synthesis of a class of 3,4-dihydro-monothiobinaphthol (3,4-H<sub>2</sub>-MTB)-derived bifunctional catalysts and their application in the asymmetric electrophilic C–H disulfuration of aza[5]helicenes. These catalysts feature a cooperative dual-activation motif: the thioether moiety acts as a Lewis base to activate the disulfurating reagent, while the phenolic hydroxyl group serves as a hydrogen-bond donor to engage the cocatalyst diphenyl phosphate. The reaction proceeds via a dynamic kinetic resolution mechanism, delivering a range of helically chiral aza[5]helicenes in good yields (up to 99%) and high enantioselectivities (up to 97% enantiomeric excess). The resulting enantioenriched products can be readily converted into helically chiral thiophenols, silyl sulfides, thioesters, and other derivatives. Mechanistic studies, including control experiments and density functional theory calculations, reveal that enantiocontrol arises from a synergistic network of noncovalent interactions including O–H···O hydrogen bonding, C–H···O interactions, and multiple C–H···π interactions facilitated by the 3,4-dihydro-binaphthyl framework. These features enable the in situ assembly of a chiral Lewis base/Brønsted acid catalytic manifold, which is instrumental in governing the observed enantioselectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20700–20711"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092021","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}
引用次数: 0
The Chameleon Role of Interfacial Hydroxyls: Reaction-Condition-Dependent Dynamics in Methanol Electro-Oxidation 界面羟基的变色龙作用:甲醇电氧化反应条件依赖动力学
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-02 DOI: 10.1021/acscatal.6c06067
Hongkai Bu, Yang-Gang Wang
{"title":"The Chameleon Role of Interfacial Hydroxyls: Reaction-Condition-Dependent Dynamics in Methanol Electro-Oxidation","authors":"Hongkai Bu,&nbsp;Yang-Gang Wang","doi":"10.1021/acscatal.6c06067","DOIUrl":"10.1021/acscatal.6c06067","url":null,"abstract":"<p>The electrocatalytic oxidation of methanol on platinum represents a model system for alcohol fuel-cell chemistry, yet the precise role of interfacial hydroxyl (OH*), a key oxidative species, remains contentious and is often viewed simplistically as either a co-reactant or a poison. Herein, ab initio molecular dynamics simulations with explicit solvation were employed to transcend this binary perspective, revealing OH* as a dynamic interfacial mediator whose coverage influences methanol activation and mechanistic pathways. Under oxidative potentials, increasing OH* coverage leads to the formation of an interfacial adsorbate layer interconnected by hydrogen bonds. Frequent proton transfer within this layer facilitates spontaneous O–H bond cleavage of methanol, while fluctuations in the hydrogen-bond network further promote its pre-oxidation and activation. In contrast, OH*-mediated C–H oxidation involves a high free-energy barrier, and increasing OH* coverage reduces the availability of Pt sites required for C–H dissociation, potentially contributing to surface poisoning. Importantly, site competition induced by high OH* coverage also alters the configuration of the reaction-generated HCHO intermediate, reducing the accessibility of further C–H cleavage toward CO* while enabling direct reaction with OH* toward formate through a CO*-free pathway. Together, these results reveal a coverage-dependent trade-off among O–H activation, the availability of Pt sites for C–H bond cleavage, and subsequent pathway selection. Regulating interfacial OH* coverage therefore provides a possible means to tune methanol oxidation activity and pathway selectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20645–20654"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092029","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}
引用次数: 0
Selective Cleavage of Carbon–Carbon Bonds of Aryl Ketones by Photocatalysis 芳基酮碳-碳键的光催化选择性裂解
IF 13.6 1区 化学
ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-06 DOI: 10.1021/acscatal.6c05776
Hao-Yuan Li, Xiu-Long Yang, Ke-Hang Zhang, Xiaoying Niu, Qing-Yuan Meng
{"title":"Selective Cleavage of Carbon–Carbon Bonds of Aryl Ketones by Photocatalysis","authors":"Hao-Yuan Li,&nbsp;Xiu-Long Yang,&nbsp;Ke-Hang Zhang,&nbsp;Xiaoying Niu,&nbsp;Qing-Yuan Meng","doi":"10.1021/acscatal.6c05776","DOIUrl":"10.1021/acscatal.6c05776","url":null,"abstract":"<p>Selective cleavage of inert C─C bonds in unstrained molecules under mild conditions remains a long-standing challenge in synthetic chemistry. In preorganized unstrained aryl ketones, Ar─C(O) bonds are particularly recalcitrant because of their high bond dissociation energy and low polarization, and their selective activation typically requires strained rings, directing groups, or harsh conditions. Here, we report a visible-light-driven triplet energy-transfer strategy that enables selective cleavage of the Ar─C(O) bond in these preorganized aryl ketones through intramolecular 1,3-acyl migration, thereby providing direct access to aliphatic ketones embedded in 9,10-dihydrophenanthrene scaffolds under mild conditions. Mechanistic experiments and density functional theory (DFT) calculations support a sequence involving triplet-state 6π photocyclization, dearomatization, and rearomatization-driven 1,3-acyl migration. This work provides a conceptually distinct photochemical solution to Ar─C(O) bond cleavage in preorganized unstrained aryl ketones and highlights rearomatization-enabled acyl migration as a useful design principle for C─C bond activation.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20586–20595"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092420","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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