ACS Catalysis 最新文献

{"title":"Complex Speciation of bipy- and phen-NNP Pincer Complexes of Ruthenium under Catalytic Ester Reduction Conditions","authors":"Daria B. Sherstiukova, Louise N. Dawe, Eugene Khaskin, Dmitry G. Gusev","doi":"10.1021/acscatal.5c04326","DOIUrl":"https://doi.org/10.1021/acscatal.5c04326","url":null,"abstract":"The N-heterocyclic backbone of NNP pincer ligands derived from 2,2′-bipyridine and 1,10-phenanthroline is prone to hydrogenation under H₂ or in alcohols. The new complex of this work, RuHCl(CO)[phen-NNP] (4), where phen-NNP = 2-((di-t-butylphosphaneyl)methyl)-1,10-phenanthroline, undergoes dearomatization when treated with potassium tert-butoxide. The dearomatized product 5 reacts with ethanol and dihydrogen to give 16-electron hydrides 7–9 containing partially hydrogenated phen-NNP ligands. The structure and reactivity of complexes 5–9 are detailed in the present report. Similar chemical behavior has been documented for the Milstein catalyst, RuHCl(CO)[bipy-NNP] where bipy = 6-((di-t-butylphosphaneyl)methyl)-2,2′-bipyridine. The dearomatized Milstein catalyst (1) is readily hydrogenated in solution at room temperature to give the main product 2 containing an NNP ligand with the central piperidine fragment, accompanied by the dimer 3 possessing one NNP ligand with an outer piperidine fragment. The dearomatized bipy- and phen-NNP complexes 1 and 5 and their hydrogenated derivatives 2, 3, and 9 were tested in this work in solventless room-temperature reduction of methyl hexanoate to hexanol under 50 bar H₂ while using a 5000:1 substrate-to-catalyst ratio. The phen-NNP derived complexes 5 and 9 proved inactive in this reaction. The density functional theory (DFT) calculations indicated that H₂ addition to the 16-electron 9 should be endoergic by at least 8.5 kcal/mol, thus, making the complex unable to transfer H₂ to the substrate. With the Milstein catalyst 1 and its hydrogenated derivatives 2 and 3 the order of activity in room-temperature reduction of methyl hexanoate was 3 > 1 > 2 with the conversions reaching 99, 70, and 34%, respectively. A distinct induction period observed in this reaction with 1 suggested that the catalytic activity should be attributed to a highly active complex catalyst formed from 1 in the reaction solution. A possible structure for this “super-catalyst” is proposed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931320","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":"Redox Heterocluster-Based Frameworks for One-Pot Photocatalytic C(sp3)-H Bond Oxidative Imination","authors":"Yu-Yang Liu, Shan Xu, Xiao-Xin Li, Run-Han Li, Xin-Ting Cai, Hui-Zhen Zhong, Jiang Liu, Qing Huang, Lei Zhang, Shun-Li Li, Ya-Qian Lan","doi":"10.1021/acscatal.5c02626","DOIUrl":"https://doi.org/10.1021/acscatal.5c02626","url":null,"abstract":"Developing strategies and photocatalysts for C(sp³)-H bond functionalization under simple and mild conditions is important but challenging. Here, we report two redox heterocluster-based frameworks, named Ni₅-PW₁₂ and Ni₅-V₁₆, in which the terminal oxygen atoms of polyoxometalates are directly coordinated to metal atoms in metal–organic clusters. Due to the coexisting strong oxidation and reduction capacities, both of these photocatalysts achieve photocatalytic C(sp³)-H bond oxidative imination through combining oxidation of methyl aromatics and reduction of nitro aromatics reactions. The experimental and theoretical results reveal that benefiting from the short distance between the clusters, the rapid charge transfer and mass transfer processes would enhance the photocatalytic reactivity and inhibit side reactions. More importantly, all of the photocatalytic reactions are carried out in mild conditions at room temperature without any additional solvents, photosensitizers, oxidizing or reducing agents, or cocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931323","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":"Ligand-Controlled Regiodivergent Double Hydroboration of Pyridines: A Catalytic Platform for the Synthesis of Diverse Functionalized Piperidines","authors":"Ruibin Wang, Seung Hyun Lee, Xinlan Huang, Hyoju Choi, Dongwook Kim, Mu-Hyun Baik, Sehoon Park","doi":"10.1021/acscatal.5c04997","DOIUrl":"https://doi.org/10.1021/acscatal.5c04997","url":null,"abstract":"Regiodivergent multiple hydroelementation of pyridines is a potentially powerful method to straightforwardly provide a diverse array of functionalized piperidines having C(sp³)–[E] bond(s) (E ≠ H). However, such regiodivergent consecutive additions of H[E] (E = Bpin, SiEt₃, etc.) to pyridines have remained unknown to date. In this study, we report the regiodivergent triple hydroelementation of pyridines, enabled by Rh-catalyzed regiodivergent double hydroboration followed by hydroelementation (E = H or P), which selectively produces two pairs of multifunctionalized piperidine isomers. Additionally, asymmetric double hydroboration of pyridines using chiral phosphine ligands has been achieved, offering a route to multifunctionalized chiral piperidines. Experimental mechanistic investigations into the regiodivergent double hydroboration reveal the formation of two distinct Rh catalytic species, dependent on the phosphine ligands employed. Computational studies corroborate these findings, elucidating the divergent catalyst initiation pathways and the mechanism of C(sp³)–B bond formation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931248","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 Asymmetric Aldol Reaction of Nonactivated Ketones with α-Isocyanocarboxylic Acid Derivatives Enabled by Prolinol-phosphine-sec-amine Chiral Ligand","authors":"Satoshi Sakai, Kei Uchiyama, Koji Imai, Kazuna Yato, Mai Onizawa, Kosuke Higashida, Hiroyasu Sato, Yoshitaka Aoyama, Yohei Shimizu, Masaya Sawamura","doi":"10.1021/acscatal.5c04986","DOIUrl":"https://doi.org/10.1021/acscatal.5c04986","url":null,"abstract":"The catalytic asymmetric aldol reaction of nonactivated ketones is a formidable challenge in asymmetric catalysis. To this end, we designed and synthesized a prolinol-phosphine-sec-amine P,N,N,O-tetradentate chiral ligand that enabled a highly diastereo- and enantioselective silver(I)-catalyzed aldol reaction of nonactivated ketones with isocyanoacetamides, affording enantioenriched α-amino acid derivatives with a tertiary alcohol at the β-position. This stereoselective reaction allowed extremely challenging molecular transformations with sterically demanding dialkyl ketones and alkyl aryl ketones, such as tert-alkyl methyl ketones, sec-alkyl primary alkyl ketones, and sec-alkyl aryl ketones. The silver(I) catalyst system was also effective in the enantiocontrolled construction of consecutive tetrasubstituted stereogenic carbon centers through the aldol reaction between simple aryl alkyl ketones and α-alkyl-α-isocyanoaetates. Spectroscopic and microED analysis combined with computational investigations showed that P,N,N,O-tetradentate metal binding of the chiral ligand allows the creation of a metal/organo cooperative asymmetric catalytic space that provides densely accumulated classical and nonclassical hydrogen bonds and complementary London dispersion interactions, stabilizing the transition state of the stereochemistry-determining ring-closing reaction of the oxyanion intermediate.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"161 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931249","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":"Synthesis of 1,4-Butanediol via One-Step Esterification–Hydrogenation of Succinic Anhydride over Cu-ZnO Catalysts: A Mechanism Study of Reaction and Deactivation","authors":"Fan Sun, Huijiang Huang, Shuo Cao, Yabo Yan, Wei Liu, Yan Xu, Rui Cheng, Yarong Su, Yang Gao, Haoye Li, Xin Tan, Yong Zhai, Bo Peng, Yujun Zhao","doi":"10.1021/acscatal.5c04456","DOIUrl":"https://doi.org/10.1021/acscatal.5c04456","url":null,"abstract":"Stable production of 1,4-butanediol (BDO) via one-step esterification–hydrogenation (OEH) of succinic anhydride (SA) was achieved over Cu-ZnO catalysts in a fixed-bed reactor. Based on the variation tendency in the stability tests and the results of XRD, ICP-OES, TEM, quasi-in situ XPS, and quasi-in situ XAS of the catalysts before and after the reaction, the reconstruction of Cu-ZnO induced by the intermediate monomethyl succinate (MMSA) was further confirmed, and the effective active site Cu⁺ was responsible for the adsorption and activation of the ester group. Combining with the different stability results of SA to BDO, succinic acid to BDO, and dimethyl succinate (DMS) to BDO, a reaction pathway for OEH of SA/succinic acid to BDO proceeded via the intermediate MMSA instead of DMS. In situ IR spectra further revealed the reaction pathway of hydrogenation of DMS, MMSA, and succinic acid on Cu-ZnO, and the deactivation mechanism of Cu-ZnO in DMS hydrogenation─formation and adsorption of polyesters on Cu⁺. This study could provide some valuable clues for fabricating highly efficient and stable Cu-based catalysts for the one-step production of BDO from SA or succinic acid.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931270","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-Hydride-Catalyzed Hydroalkylation of Cyclic Phosphinates: Generation of Enantioenriched Phosphorus and Carbon Stereocenters","authors":"Lara Lavrencic, Uttam Dhawa, Xile Hu","doi":"10.1021/acscatal.5c04286","DOIUrl":"https://doi.org/10.1021/acscatal.5c04286","url":null,"abstract":"In contrast to numerous examples leveraging Ni–H catalysis for the construction of a single or two adjacent stereocenters, accessing two stereoenriched 1,3-chiral centers has so far remained underexplored. Furthermore, Ni–H chemistry is yet to be extended beyond the construction of chirality at carbon. Herein, we report a Ni–H catalyzed dynamic kinetic asymmetric transformation of cyclic phosphinates, furnishing compounds with two nonadjacent stereocenters. Interconversion of P-chiral substrate enantiomers is achieved by fast and reversible migration of the alkene double bond, resulting in high levels of reaction enantio-, diastereo- and regioselectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"68 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931271","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":"Controlling Acid Sites in Atomically Precise Cu/Al2O3 Clusters for Selective Methanol Production from CO2 Hydrogenation","authors":"Seongmin Jin, Yu-Cheng Lin, Bartu Karakurt, Tom Nelis, Mark Tanchev, Laura Piveteau, Mounir Driss Mensi, Aram Bugaev, Olga Safonova, Jeremy S. Luterbacher","doi":"10.1021/acscatal.5c04952","DOIUrl":"https://doi.org/10.1021/acscatal.5c04952","url":null,"abstract":"Creating low-nuclearity moieties on the order of 10 metal atoms presents an opportunity to exert control over their electronic properties, thereby tuning their catalytic behavior. We designed an atomic cluster catalyst (Cu/MgOAl₂O₃) comprising small Al₂O₃ clusters in contact with Cu species via liquid-phase atomic layer deposition (ALD) with near-atomic precision. Upon the reduction of Cu in Cu/MgOAl₂O₃, direct interactions between Cu and Al atoms occurred in a low nuclearity cluster (Cu/Al₂O₃), leading to alterations in their electron densities. This interaction resulted in a reduced Lewis acidic strength of Al atoms on a basic MgO support compared with the strong Lewis acidity found from the bulk Al₂O₃-supported Cu catalyst (Cu/Al₂O₃). Modulating Lewis acidity in this way effectively tuned the adsorption strength of the reaction intermediates during the hydrogenation of CO₂ to methanol, achieving a methanol selectivity of 59%. Moreover, Cu/MgOAl₂O₃ exhibited approximately 9 and 3 times higher space-time-yield (STY) compared to Cu/Al₂O₃ and Cu/MgO, respectively. In contrast, the strong binding of acetate and methoxy species on Cu/Al₂O₃ caused surface poisoning, limiting its methanol selectivity to 20%. This study establishes that the formation of small metal oxide clusters can introduce controlled complexity to active sites, offering a method for designing multifunctional catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"32 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931250","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":"Enzymatic Strategies for Next-Generation DNA Synthesis: Boosting Efficiency and Overcoming Secondary Structures","authors":"Nico D. Fessner","doi":"10.1021/acscatal.5c05189","DOIUrl":"https://doi.org/10.1021/acscatal.5c05189","url":null,"abstract":"Chemical DNA synthesis is the gold standard for producing synthetic oligonucleotides. Despite four decades of success, fragment length and secondary DNA structure formation remain limitations, constraining access to long, complex sequences. Enzymatic de novo DNA synthesis has emerged as a promising next-generation alternative, offering a catalytic nature, higher coupling efficiencies, and uninterrupted strand growth. Recent advances, such as Codexis’ evolved terminal deoxynucleotidyl transferase (TdT) achieving near-chemical coupling efficiencies with 3′-phosphate-protected nucleotides, show that enzyme engineering is a viable path forward. The mitigation of secondary DNA structure formation is equally crucial to avoid synthesis stalls and complicated DNA assembly yet it remains surprisingly underexplored. This Perspective highlights current strategies to address both bottlenecks: improving TdT catalysis and controlling DNA folding. Together, these efforts could enable routine, cost-effective synthesis of kilobase-long, structure-rich sequences, transforming research and industrial applications alike.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"19 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144987299","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":"Anchoring Pd onto Sn Sites in Zeolite Framework for Baeyer–Villiger Oxidation with H2 and O2","authors":"Chengwei Zhai, Shiqing Li, Yaqi Fan, Jie Tuo, Xianchen Gong, Teng Yang, Zhipeng Wan, Yue Ma, Yanhang Ma, Peng Wu, Hao Xu","doi":"10.1021/acscatal.5c04848","DOIUrl":"https://doi.org/10.1021/acscatal.5c04848","url":null,"abstract":"Incorporating precious metals into heteroatom-containing zeolites not only enhances metal dispersion but also unlocks the application potential of zeolite catalysts, facilitating the development of bifunctional catalytic systems. We successfully synthesized a bifunctional catalyst via a simple impregnation approach in which palladium (Pd) was confined within the channels of Sn-Beta zeolite. This resultant Pd@Sn-Beta catalyst enables the Baeyer–Villiger (B–V) oxidation of ketone to the corresponding lactone through the in situ generation of hydrogen peroxide (H₂O₂) from hydrogen (H₂) and oxygen (O₂). The characterizations with EPR and in situ DRIFTS confirmed the formation of ^•OOH radical over Pd species, which is subsequently transformed to H₂O₂ during the catalytic process. XPS and X-ray absorption fine structure analyses revealed a strong interaction between the dual active sites of Sn and Pd. The proximity of Pd and Sn active sites shortens the diffusion pathway of in situ formed H₂O₂ and prevents unproductive decomposition, thereby ensuring high B–V reaction activity. Using 2-adamantanone as a substrate, a remarkable ketone conversion rate (88%) and lactone selectivity (99%) were achieved with an optimal Pd@Sn-Beta catalyst. These findings highlight the potential of heteroatom-containing zeolites as supports for developing highly dispersed metal catalysts, offering more opportunities for their catalytic applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"141 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928683","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":"Transforming Waste Biomass into N-Rich Carbon Dots with Built-In Active Sites for Efficient CO2 Photoreduction from Flue Gas","authors":"Ganghua Zhou, Chuanzhou Bi, Xin Qian, Yanglin Chen, Hailong Liu, Xin Ning, Can Xue, Penghui Ding, Xiaozhi Wang, Xingwang Zhu","doi":"10.1021/acscatal.5c04589","DOIUrl":"https://doi.org/10.1021/acscatal.5c04589","url":null,"abstract":"The direct conversion of CO₂ from simulated flue gas to chemical feedstock gases using solar energy remains a significant challenge. A fundamental difficulty is the design of catalyst surfaces with high CO₂ affinity and the improvement of photocatalytic accumulation efficiency. Herein, we developed a facile synthesis strategy to prepare model anatase photocatalyst (Ti-EBCD) surface-functionalized with waste-biomass-derived carbon dot (EBCD) for CO₂ conversion. Importantly, the abundant functional groups and intrinsically active pyridinic-N sites in Ti-EBCD construct a CO₂-affinitive surface, thereby enhancing the CO₂ adsorption and activation. The optimized Ti-EBCD catalyst not only achieves a tunable syngas conversion with pure CO₂ but also exhibits high CO selectivity during simulated flue gas conversion. A series of characterizations, in situ experiments, and theoretical calculations were employed to establish structure–activity relationships and reveal the reaction mechanisms behind the enhanced selective conversion of simulated flue gas. We anticipate that this work will provide insights into the development of advanced surface-engineered photocatalysts for solar-driven simulated flue gas conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928684","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}