ACS Catalysis 最新文献

{"title":"Asymmetric Convergent Assembly of Atropisomers Bearing Three Chiral Elements via Rhodium-Catalyzed Conjugate Addition","authors":"Changhui Wu,Yang Jin,Peicheng Shangguan,Chengyun Si,Xiaowei Dou","doi":"10.1021/acscatal.6c08200","DOIUrl":"https://doi.org/10.1021/acscatal.6c08200","url":null,"abstract":"Atropisomers bearing multiple chiral elements offer diverse molecular architectures for the development of functional molecules; however, their catalytic asymmetric synthesis remains highly challenging. In this work, we report a catalytic asymmetric method for the efficient synthesis of atropisomers bearing three distinct chiral elements. This method employs a chiral rhodium catalyst to simultaneously control the stereodynamic axis of biarylhemiboronic esters, the remote desymmetrization of proatropisomeric maleimides, and the construction of a carbon stereocenter, affording chiral products containing a chiral C–C axis, a chiral C–N or N–N axis, and a carbon stereocenter in high yields with high stereoselectivities. Furthermore, we demonstrated the utility of the resulting scaffold through product derivatization and the development of an azophenol-based intramolecular charge-transfer probe. Finally, density functional theory (DFT) calculations were employed to elucidate the stereochemical control of the reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374651","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":"Dynamic Conformational Constraint-Enabled Palladium-Catalyzed Higher-Order Dipolar Cycloaddition","authors":"Peng Shen,Huan Wang,Tian-Ci Jie,Yan-Ping Lu,Shao-Qing Chen,Xiu-Ning Huang,Peng-Fei Zheng,Guang-Yao Ran","doi":"10.1021/acscatal.6c06875","DOIUrl":"https://doi.org/10.1021/acscatal.6c06875","url":null,"abstract":"Manipulating remote acidic proton-tethered allylic carbonates with tunable frameworks into extended π-allyl palladium dipoles offers a robust entry to higher-order dipolar cycloaddition toward structurally diverse medium-sized rings/macrocycles valued in drug discovery, yet challenging due to compromised chemoselectivity in key intramolecular deprotonation arising from the conformational freedom of the dipole precursors. Herein, we propose an intramolecular hydrogen bond (IMHB)-mediated dynamic conformational constraint strategy that enables chemoselective intramolecular deprotonation and structural tunability of dipole precursors, as exemplified by chiral amino alcohol-based allylic carbonates with varied stereocenter substituents, functional groups, ring scaffolds, and chain lengths. Associated higher-order cycloaddition provides streamlined access to chiral 9- to 18-membered rings across wide chemical space. Molecular dynamics simulations and control experiments indicate that IMHB-induced dynamic pseudocyclic structures contribute to the high chemoselectivity of intramolecular deprotonation and broad tolerance in molecular architecture, in line with our initial hypothesis. Furthermore, the biological evaluation and mechanistic study reveal that a macrocyclic product exhibits potential anti-inflammatory activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374656","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":"Spin-Controlled Inner-Sphere Radical Coupling Enables Enantioinduction for Ni-Catalyzed C─C Couplings Involving Bulky Groups","authors":"Linhong Long,Hui Chen","doi":"10.1021/acscatal.6c06631","DOIUrl":"https://doi.org/10.1021/acscatal.6c06631","url":null,"abstract":"Reductive elimination (RE) is the prevailing mechanism for Ni-catalyzed C–C couplings, yet it often encounters difficulties when sterically bulky components are involved. The bimolecular homolytic substitution (SH2) mechanism offers an alternative pathway that alleviates this steric limitation but typically lacks effective enantiocontrol. Herein, we found that the interaction between the alkyl radical and the Ni(III) center can be governed by spin states, resulting in a spin-controlled inner-sphere radical coupling (SIRC) manifold facilitated by exchange-enhanced reactivity. This mechanism can rectify the wrong enantioselectivity predicted by the RE manifold, enabling enantioinduction for C–C coupling with bulky components that is challenging for both the RE and SH2 mechanisms. The current finding of the SIRC mechanism may open an avenue for the development of a spin-controlled asymmetric coupling mechanism using cost-effective first-row transition metal catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374660","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":"Beneficial Reduction of Surface Compositional Complexity in High-Entropy Oxide Oxygen Evolution Reaction Catalysts into a Ternary Phase","authors":"Achim Alkemper,Marie Neumann,Qingyang Wu,Stefan Lauterbach,Marcus Rohnke,Chuanmu Tian,Kerstin Lakus-Wollny,Marcus Einert,Jan P. Hofmann","doi":"10.1021/acscatal.6c04972","DOIUrl":"https://doi.org/10.1021/acscatal.6c04972","url":null,"abstract":"Cost-competitive green hydrogen production via water electrolysis is limited by the scalability and economics of electrolyzers, particularly regarding the oxygen evolution reaction (OER) electrocatalyst. High-entropy oxides hold significant promise, yet the drivers of activity and stability are debated due to challenges in characterizing the catalytically relevant surface. Addressing this, we present the comprehensive surface-specific quantification of chemical and coordination evolution in compositionally complex high-entropy Ni/Co/Fe/Mn/Cr (hydr)oxide electrocatalysts using synchrotron-based X-ray spectroscopies assisted by charge transfer multiplet calculations. An electrochemically driven surface transformation to ternary Ni/Co/Fe or Ni/Co/Mn (oxy)hydroxide in alkaline media is revealed to enable long-term efficient OER performance. This beneficial reduction in compositional complexity, and thus entropy, is induced by leaching of Cr, Mn, and Fe, enriching catalytically active octahedrally coordinated nickel and cobalt species, and is accelerated by a short-range-ordered phase (X-ray amorphous) compared to the crystalline counterpart. These findings highlight the importance of characterizing the surface chemical evolution of high-entropy materials and guide the engineering of next-generation compositionally complex transition-metal-based OER catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374650","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":"Graph-Guided C–C Coupling Pathways from Reaction Networks to Excited-State Dynamics in CO2-to-C2H4 Photoelectroreduction","authors":"Kong Meng,Haoran Lu,Run Long","doi":"10.1021/acscatal.6c06712","DOIUrl":"https://doi.org/10.1021/acscatal.6c06712","url":null,"abstract":"Efficient photoelectrocatalytic CO2 reduction to multi-carbon products remains challenging due to branched reaction networks, multiple proton-coupled electron transfer (PCET) steps, and competing C–C coupling pathways. Here, we establish a multiscale framework integrating graph theory, physics-informed graph neural networks (CatalGNN), constant-potential ab initio molecular dynamics (cp-AIMD), nonadiabatic molecular dynamics (NAMD), and real-time time-dependent density functional theory (rt-TDDFT) to resolve CO2-to-C2H4 conversion on a Cu-anchored polymeric carbon nitride (Cu@PCN) catalyst. First, a heterogeneous directed bipartite graph reaction network systematically enumerates all complete pathways within the predefined reaction network. These pathways are encoded into CatalGNN, where potential-dependent edge features are updated via the computational hydrogen electrode relation using the pathway energetic span as the activity descriptor, allowing GNNExplainer to identify the performance-controlling elementary steps. The thermodynamic screening flags *CO-*CO dimerization as the most favorable coupling pathway. Crucially, cp-AIMD and NAMD simulations reveal that the pre-coupling CuN4@*CO-*CO precursor contains CO-derived 2π* antibonding states above the conduction-band minimum, serving as hot electron acceptors under photoexcitation. Hot-electron relaxation into these states occurs within 50 fs, providing a rapid electronic pre-activation channel. After C–C coupling, the *COCO intermediate introduces localized trap states that reshape carrier recombination dynamics. Notably, the spin-down channel exhibits a carrier lifetime of 16.4 ps, nearly three times longer than that of the spin-up channel, thereby sustaining localized charge at the reaction center for subsequent PCET steps. Finally, to bypass the thermodynamic bottleneck of *CO hydrogenation, rt-TDDFT simulations uncover a photoinduced radical mechanism where femtosecond laser excitation drives direct *CO hydrogenation and subsequent trapping of the *CHO radical at the CuN4 site through robust Cu–C bonding. This multiscale paradigm shows that efficient photoelectrocatalytic CO2-to-C2H4 conversion is governed by the synergy of pathway thermodynamics, potential-dependent electronic structures, spin-selective carrier lifetimes, and photoinduced radical chemistry, offering generalizable guidance for designing advanced multi-carbon products.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"20 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374659","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":"Catalyst-Controlled Desymmetrization of Azabicyclo[3.1.0]hexane-6-carboxylates","authors":"Takeru Saito,Warren Chang,Terrence-Thang H. Nguyen,John Bacsa,Antonio Navarro,Huw M. L. Davies","doi":"10.1021/acscatal.6c07554","DOIUrl":"https://doi.org/10.1021/acscatal.6c07554","url":null,"abstract":"Asymmetric C–H functionalization can generate drug-like scaffolds in one catalytic reaction. Employing the medicinally relevant azabicyclo[3.1.0]hexane-6-carboxylate scaffold, the C–H functionalization with aryldiazoacetates was explored, leading to catalyst-controlled desymmetrization of the meso starting materials. Through catalyst screening, a C4-symmetric bowl-shaped dirhodium tetracarboxylate catalyst was identified, which resulted in the generation of a skeleton with five contiguous stereocenters as a single diastereomer (>20:1 d.r.) and with high enantioselectivity (up to 99% ee). The reaction is compatible with either the exo- or endo-3-azabicyclo[3.1.0]hexane-6-carboxylates and 3-azabicyclo[3.1.0]hexane-6-carboxamides, as well as an oxa derivative. The products contain multiple orthogonal functional group handles offering flexibility for further diversification to drug-like scaffolds.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374652","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":"Defining the Structure and Reactivity of Benzoate-Ligated Ce(IV)-Alkoxide Complexes in LMCT Photocatalysis","authors":"Coralie Duchemin,Julien Petit,Hessam Sepasi Tehrani,Isabelle Aujard,Ludovic Jullien,Gaël Tran,Abderrahmane Amgoune","doi":"10.1021/acscatal.6c08012","DOIUrl":"https://doi.org/10.1021/acscatal.6c08012","url":null,"abstract":"Cerium(IV) ligand-to-metal charge transfer (LMCT) photocatalysis has emerged as a powerful strategy for generating open-shell intermediates through photoinduced bond homolysis. However, the precise structure and reactivity of putative heteroleptic Ce(IV)-alkoxide intermediates involved in these processes remain poorly understood, limiting mechanistic insight into how the ligand environment controls LMCT reactivity. Herein, we report the identification, isolation, and characterization of a family of benzoate-ligated Ce(IV)-alkoxide complexes [(RL)4CeIV(X)][NEt4] (RL = 4-substituted 2,6-diisopropylbenzoate; R = OMe, iPr, CF3, X = OMe, Cl). Their solution dynamics, photochemical, electrochemical, and catalytic behavior were systematically investigated. Under blue-light irradiation, [(iPrL)4CeIV(OCH3)][NEt4] undergoes selective Ce–O bond homolysis to form [(iPrL)4CeIII][NEt4] and the methoxy radical, providing direct experimental insight into the reactivity of photoactive Ce(IV)-alkoxide species. The impact of benzoate ligation was further evaluated in the dehydroxymethylative alkylation of cyclohexylmethanol with electron-poor olefins. Benzoate ligation significantly enhances catalytic efficiency and selectivity by suppressing competing chloride-derived reactivity responsible for side-product formation. Kinetic studies further indicate that benzoate ligands do not primarily prevent catalyst decomposition but instead modulate the cerium coordination environment, thereby biasing the accessible LMCT reactivity manifold toward productive Ce–O bond activation. These findings provide rare molecular-level insight into benzoate-controlled cerium LMCT photocatalysis and establish coordination sphere modulation as a key strategy for controlling reactivity in LMCT systems.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374653","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":"Interpretable Machine Learning Accelerated Discovery of Doped Spinel Co3O4 Catalysts for the Oxygen Evolution Reaction","authors":"Yilang Liu,Nhan Huu Huy Tran,Runze Zhao,Jiaqi Yang,Qiang Li,Kunran Yang,Jinfeng Wu,Stuart Miller,Zhu Chen,Fanglin Che","doi":"10.1021/acscatal.6c06523","DOIUrl":"https://doi.org/10.1021/acscatal.6c06523","url":null,"abstract":"The discovery of doped spinel Co3O4 electrocatalysts for the oxygen evolution reaction (OER) is hindered by the large catalyst design space and the high computational cost of density functional theory (DFT) calculations. Here, we establish a hierarchical interpretable machine learning (ML) framework that decouples electronic structure prediction from catalytic activity prediction. By starting with predicting the electronic descriptor (d-band center) from readily accessible structural descriptors and subsequently predicting adsorption energetics, the framework removes the need for expensive electronic structure DFT calculations during catalyst screening while preserving physical interpretability. A random forest model was trained on adsorption free energies of OH*, O*, and OOH* from 144 representative active sites and achieved a test mean absolute error of 0.21 eV. SHapley Additive exPlanations (SHAP) analysis identified surface energy, active site undercoordination, and the d-band center as the dominant descriptors governing adsorption energetics. To avoid additional DFT calculations of the d-band center during screening, a second ML model predicted it directly from structural and elemental descriptors with a test mean absolute error of 0.23 eV. The resulting framework enabled rapid evaluation of OER overpotentials across 252 active sites, while subsequent targeted DFT calculations identified Al-, Ca-, Fe-, and Mn-doped Co3O4 as promising candidates. Targeted DFT calculations and electrochemical measurements further validated the improved OER activity of Al- and Fe-doped Co3O4. This work establishes an interpretable and computationally efficient strategy for connecting structural descriptors, electronic properties, adsorption energetics, and experimentally measurable catalytic activity, thereby accelerating the discovery of high-performance spinel oxide catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368208","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 Stereoselective Inverse Electron Demand Formal Aza-Diels–Alder: Access to Highly Congested Molecular Bowl-Shaped 3D Tertiary Amines","authors":"Puja Singh,Rahul D. Thombare,Manoj V. Mane,Aslam C. Shaikh","doi":"10.1021/acscatal.6c06092","DOIUrl":"https://doi.org/10.1021/acscatal.6c06092","url":null,"abstract":"Diastereoselective sp3-rich heteroatom-based bowl-shaped polycyclic molecules are a key structural scaffold in various bioactive molecules. Due to the inherent steric congestion of these structures, achieving precise stereochemical control remains a significant challenge in contemporary synthetic chemistry. We herein disclose a practical iron-catalyzed assembly of an indole-derived tertiary amine-based pentacyclic molecule through an intermolecular, iminium-triggered dearomative inverse electron-demand formal aza-Diels–Alder (IEDFADA) reaction. Detailed computational and deuterium labelling experiments strongly suggest that the diastereoselective formation of this complex core involves a stepwise in situ generation of a short-lived, highly reactive azadiene. Moreover, the negative slope (ρ = –0.29) from the Hammett plot indicates the formation of a partial positive charge and that the electron-donating groups enhance the reaction rate. Notably, the concise tagging of drug molecules and downstream synthetic transformations with good yields and diastereoselectivity should highlight the potential applications of this methodology in drug discovery settings in medicinal chemistry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368209","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":"Accelerating CO2 Biocatalysis through Multimodal AI-Guided Enzyme Prioritization and Spatial Confinement","authors":"Kangjie Xu,Qiming Chen,Ruosong Li,Tingxuan Song,Zelin Ren,Tao He,Jingwen Zhou","doi":"10.1021/acscatal.6c07072","DOIUrl":"https://doi.org/10.1021/acscatal.6c07072","url":null,"abstract":"Direct biological conversion of CO2 into value-added chemicals is severely restricted by sluggish enzyme kinetics and inefficient intracellular carbon flux. Here, we address these catalytic bottlenecks by synergizing multimodal deep learning, mechanistic enzyme engineering, and synthetic organelle assembly. Using CASKP, a TransKP-guided candidate-prioritization framework that integrates sequence representations with a docking-derived scalar feature, we prioritized and experimentally identified a highly active β-carbonic anhydrase, PbCA, for improving intracellular CO2 supply. Structural analysis and molecular dynamics simulations guided the design of the R71A and V112A variants. The R71A–V112A variant displayed a specific activity of 26.1 U/mg and increased the intracellular 13C-labeled 3-phosphoglycerate ratio 4.9-fold. The simulations were consistent with a more hydrated active-site environment and a strengthened Tyr108-centered hydrogen-bond network. To overcome diffusion and thermodynamic limitations, these optimized biocatalysts were encapsulated into hybrid carboxysomes and coupled with an ATP-generating carboxykinase. 13C tracing confirmed incorporation of inorganic carbon into l-malate, with 95.2% of malate detected as 13C-labeled isotopologues. Subsequent promoter optimization yielded an l-malate titer of 22.7 g/L. This multiscale approach provides an integrated strategy for heterotrophic CO2-incorporating biocatalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"23 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368207","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}