Nature Catalysis最新文献_第5页

The iron-catalysed Suzuki coupling of aryl chlorides 铁催化的芳基氯化物铃木偶联反应

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-10-17 DOI: 10.1038/s41929-024-01234-0

Benjamin J. S. Rowsell, Harry M. O’Brien, Gayathri Athavan, Patrick R. Daley-Dee, Johannes Krieger, Emma Richards, Karl Heaton, Ian J. S. Fairlamb, Robin B. Bedford

{"title":"The iron-catalysed Suzuki coupling of aryl chlorides","authors":"Benjamin J. S. Rowsell, Harry M. O’Brien, Gayathri Athavan, Patrick R. Daley-Dee, Johannes Krieger, Emma Richards, Karl Heaton, Ian J. S. Fairlamb, Robin B. Bedford","doi":"10.1038/s41929-024-01234-0","DOIUrl":"10.1038/s41929-024-01234-0","url":null,"abstract":"The very widely exploited Suzuki biaryl coupling reaction typically requires catalysts based on palladium, but there is an increasing desire to replace this metal with a more sustainable, less expensive alternative, with catalysts based on iron being a particularly attractive target. Here we show that a simple iron-based catalyst with an N-heterocyclic carbene ligand can be used to excellent effect in the Suzuki biaryl coupling of aryl chloride substrates with aryl boronic esters activated by an organolithium reagent. Mechanistic studies suggest the possible involvement of Fe(I) as the lowest oxidation state on the catalytic manifold and show that the challenging step is not activation of the aryl chloride substrate, but rather the transmetallation step. These findings are likely to lead to a renaissance of iron-catalysed carbon–carbon bond-forming transformations with soft nucleophilic coupling partners. The replacement of palladium with other metal catalysts in C–C bond-forming reactions is attractive in terms of costs and sustainability. Now an iron-based catalyst is successfully employed in the Suzuki cross-coupling of aryl chlorides with aryl boronic esters activated with tert-butyl lithium.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 11","pages":"1186-1198"},"PeriodicalIF":42.8,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01234-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440846","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}

引用次数: 0

Atom-by-atom design of Cu/ZrOx clusters on MgO for CO2 hydrogenation using liquid-phase atomic layer deposition 利用液相原子层沉积技术在氧化镁上逐个原子设计用于二氧化碳加氢的铜/氧化锆团簇

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-10-14 DOI: 10.1038/s41929-024-01236-y

Seongmin Jin, Choah Kwon, Aram Bugaev, Bartu Karakurt, Yu-Cheng Lin, Louisa Savereide, Liping Zhong, Victor Boureau, Olga Safonova, Sangtae Kim, Jeremy S. Luterbacher

{"title":"Atom-by-atom design of Cu/ZrOx clusters on MgO for CO2 hydrogenation using liquid-phase atomic layer deposition","authors":"Seongmin Jin, Choah Kwon, Aram Bugaev, Bartu Karakurt, Yu-Cheng Lin, Louisa Savereide, Liping Zhong, Victor Boureau, Olga Safonova, Sangtae Kim, Jeremy S. Luterbacher","doi":"10.1038/s41929-024-01236-y","DOIUrl":"10.1038/s41929-024-01236-y","url":null,"abstract":"The difficulty of synthesizing uniform atomically precise active sites limits our ability to engineer increasingly more active heterogeneous catalysts for the hydrogenation of CO2 to methanol. Here we design Cu/ZrOx clusters on MgO with near atomic precision for CO2 hydrogenation using a liquid-phase atomic layer deposition method. The controlled cluster structure modulates the binding strength of CO2 and moderately stabilizes monodentate formate—an essential reaction intermediate for methanol production. We achieved a methanol selectivity of 100 and 76.7% at 200 and 250 °C, respectively and a methanol productivity that was one to two orders of magnitude higher than when the same catalysts were prepared by impregnation. Ab initio computations show that Cu/ZrOx clusters can tune the oxidation of Zr, which controls the stability of reaction intermediates on the catalyst. Our approach demonstrates the potential of precise atomic control of catalytic clusters to improve catalytic productivity. Achieving atomic control during the synthesis of heterogeneous catalysts remains challenging. Here the authors tackle this challenge by applying a liquid-phase atomic layer deposition approach to the synthesis of Cu/ZrOx clusters on MgO as efficient catalysts for CO2 hydrogenation to methanol.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 11","pages":"1199-1212"},"PeriodicalIF":42.8,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430570","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

Iron-catalysed cooperative redox mechanism for the simultaneous conversion of nitrous oxide and nitric oxide 铁催化的同时转化一氧化二氮和一氧化氮的合作氧化还原机制

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-10-10 DOI: 10.1038/s41929-024-01231-3

Filippo Buttignol, Jörg W. A. Fischer, Adam H. Clark, Martin Elsener, Alberto Garbujo, Pierdomenico Biasi, Izabela Czekaj, Maarten Nachtegaal, Gunnar Jeschke, Oliver Kröcher, Davide Ferri

{"title":"Iron-catalysed cooperative redox mechanism for the simultaneous conversion of nitrous oxide and nitric oxide","authors":"Filippo Buttignol, Jörg W. A. Fischer, Adam H. Clark, Martin Elsener, Alberto Garbujo, Pierdomenico Biasi, Izabela Czekaj, Maarten Nachtegaal, Gunnar Jeschke, Oliver Kröcher, Davide Ferri","doi":"10.1038/s41929-024-01231-3","DOIUrl":"10.1038/s41929-024-01231-3","url":null,"abstract":"Iron-exchanged zeolites are often deployed industrially to remediate nitric oxide (NO) and nitrous oxide (N2O) emissions. The nature of the active site and the reaction mechanism involved in the simultaneous removal of NO and N2O remain largely unknown, primarily because of the heterogeneity of Fe species. Here we combined catalytic experiments with transient operando X-ray absorption spectroscopy, electron paramagnetic resonance and diffuse reflectance infrared Fourier transform spectroscopy to disentangle the nature of Fe species and elementary reaction steps. We identified spectroscopically the square-planar Fe2+ sites in the β-cationic position responsible for N2O activation and the related redox cycle. These sites communicate with tetrahedrally coordinated Fe2+ sites in the adjacent γ-cationic position, accounting for adsorption and redox-mediated oxidation of NO. The availability of NH3 adsorbed on neighbouring Brønsted acid sites regulates the overall reaction rate of this dual-site mechanism by intercepting the NO oxidation sequence. The cooperation between these redox processes ensures enhanced conversion of both NO and N2O. Fe-exchanged zeolite catalysts are known for their ability to remediate NOx and N2O emissions, but their reactivity in mixed streams of NO and N2O remains unclear. Now a suite of operando spectroscopies reveals the active Fe species involved in the process and their synergistic effect during the simultaneous conversion of these pollutants.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1305-1315"},"PeriodicalIF":42.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398246","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

Organocatalytic asymmetric α-C–H functionalization of alkyl amines 烷基胺的有机催化不对称 α-C-H 功能化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-10-03 DOI: 10.1038/s41929-024-01230-4

Tianran Deng, Xiang-Lei Han, Yang Yu, Cheng Cheng, Xiangyuan Liu, Yuhong Gao, Keqiang Wu, Zhenghua Li, Jisheng Luo, Li Deng

{"title":"Organocatalytic asymmetric α-C–H functionalization of alkyl amines","authors":"Tianran Deng, Xiang-Lei Han, Yang Yu, Cheng Cheng, Xiangyuan Liu, Yuhong Gao, Keqiang Wu, Zhenghua Li, Jisheng Luo, Li Deng","doi":"10.1038/s41929-024-01230-4","DOIUrl":"10.1038/s41929-024-01230-4","url":null,"abstract":"Catalytic enantioselective α-C–H functionalization of widely available achiral alkyl amines could provide an ideal synthetic approach towards chiral amines. However, the inert nature of the α-C–H of alkyl amines renders their activation as carbanionic nucleophiles for catalytic asymmetric reactions an important yet unmet challenge. Here we describe how N-arylidene-protected alkyl amines could be activated as carbanions for asymmetric conjugate addition and the Mannich reaction. These results represent an intriguing and generally useful approach to the synthesis of chiral α,α-dialkyl amines. More importantly, they highlight the enormous potential of N-arylidene-protected amines as readily available and widely applicable synthons for the asymmetric synthesis of chiral amines. The catalytic activation of alkyl amines as α-nitrogen carbanions is challenging. Now the activation of N-arylidene-protected alkyl amines as carbanions by chiral ammonium organocatalysis for asymmetric conjugate addition and the Mannich reaction is reported, affording chiral α,α-dialkyl amines.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1076-1085"},"PeriodicalIF":42.8,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142368994","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

Author Correction: Localized thermal levering events drive spontaneous kinetic oscillations during CO oxidation on Rh/Al2O3 作者更正：局部热杠杆事件驱动 Rh/Al2O3 上 CO 氧化过程中的自发动力学振荡

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-10-03 DOI: 10.1038/s41929-024-01240-2

Donato Decarolis, Monik Panchal, Matthew Quesne, Khaled Mohammed, Shaojun Xu, Mark Isaacs, Adam H. Clark, Luke L. Keenan, Takuo Wakisaka, Kohei Kusada, Hiroshi Kitagawa, C. Richard A. Catlow, Emma K. Gibson, Alexandre Goguet, Peter P. Wells

引用次数: 0

Directed evolution of a highly efficient TNA polymerase achieved by homologous recombination 通过同源重组实现高效 TNA 聚合酶的定向进化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-10-01 DOI: 10.1038/s41929-024-01233-1

Victoria A. Maola, Eric J. Yik, Mohammad Hajjar, Joy J. Lee, Manuel J. Holguin, Riley N. Quijano, Kalvin K. Nguyen, Katherine L. Ho, Jenny V. Medina, Nicholas Chim, John C. Chaput

{"title":"Directed evolution of a highly efficient TNA polymerase achieved by homologous recombination","authors":"Victoria A. Maola, Eric J. Yik, Mohammad Hajjar, Joy J. Lee, Manuel J. Holguin, Riley N. Quijano, Kalvin K. Nguyen, Katherine L. Ho, Jenny V. Medina, Nicholas Chim, John C. Chaput","doi":"10.1038/s41929-024-01233-1","DOIUrl":"10.1038/s41929-024-01233-1","url":null,"abstract":"Reprogramming DNA polymerases to synthesize xeno-nucleic acids (XNAs) is an important challenge that tests current enzyme engineering tools. Here we describe an evolutionary campaign aimed at generating an XNA polymerase that can efficiently make α-l-threofuranosyl nucleic acid (TNA)—an artificial genetic polymer that is recalcitrant to nucleases and resistant to acid-mediated degradation. Starting from a homologous recombination library, iterative cycles of selection were performed to traverse the fitness landscape in search of neutral mutations with increased evolutionary potential. Subsequent directed evolution of focused mutagenic libraries yielded 10–92, a newly engineered TNA polymerase that functions with a catalytic rate of ∼1 nt s−1 and >99% fidelity. A crystal structure of the closed ternary complex reveals the degree of structural change required to remodel the active site pocket for improved TNA synthesis activity. Together, these data demonstrate the importance of recombination as a strategy for evolving XNA polymerases with considerable practical value for biotechnology and medicine. The catalytic power of DNA polymerases for artificial genetic polymer (XNA) synthesis remains underdeveloped. Now, the evolution and structure of an α-l-threofuranosyl nucleic acid polymerase is described that achieves XNA synthesis with ∼1 nt s−1 and >99% template-copying fidelity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 11","pages":"1173-1185"},"PeriodicalIF":42.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142330403","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

Step bunching instability and its effects in electrocatalysis on platinum surfaces 铂表面阶跃束化不稳定性及其对电催化的影响

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-30 DOI: 10.1038/s41929-024-01232-2

Francesc Valls Mascaró, Marc T. M. Koper, Marcel J. Rost

{"title":"Step bunching instability and its effects in electrocatalysis on platinum surfaces","authors":"Francesc Valls Mascaró, Marc T. M. Koper, Marcel J. Rost","doi":"10.1038/s41929-024-01232-2","DOIUrl":"10.1038/s41929-024-01232-2","url":null,"abstract":"The atomic-scale surface structure plays a major role in the electrochemical behaviour of a catalyst. The electrocatalytic activity towards many relevant reactions, such as the oxygen reduction reaction on platinum, exhibits a linear dependency with the number of steps until this linear scaling breaks down at high step densities. Here we show, using Pt(111)-vicinal surfaces and in situ electrochemical scanning tunnelling microscopy, that this anomalous behaviour at high step densities has a structural origin and is attributed to the bunching of closely spaced steps. While Pt(554) presents parallel single steps and terrace widths that correspond to its nominal, expected value, most steps on Pt(553) are bunched. Our findings challenge the common assumption in electrochemistry that all stepped surfaces are composed of homogeneously spaced steps of monoatomic height and can successfully explain the anomalous trends documented in the literature linking step density to both activity and potential of zero total charge. The electrocatalytic activity of metal catalysts commonly exhibits a positive linear correlation with the presence of steps, but this dependency breaks down for Pt catalysts with high step densities. Now, using in situ electrochemical scanning tunnelling microscopy, it is shown that this is due to the bunching of closely spaced steps, forming double and triple steps.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 11","pages":"1165-1172"},"PeriodicalIF":42.8,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329493","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

Without that crystalline touch 没有那晶莹剔透的触感

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01222-4

Xiaofei Guan

引用次数: 0

Deciphering electrochemical methanol production 解密电化学甲醇生产

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01224-2

Stefan Ringe

引用次数: 0

Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer 通过单电子转移实现 sp3 C-H 功能化的金属光氧催化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01215-3

Jingchang Zhang, Magnus Rueping

{"title":"Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer","authors":"Jingchang Zhang, Magnus Rueping","doi":"10.1038/s41929-024-01215-3","DOIUrl":"10.1038/s41929-024-01215-3","url":null,"abstract":"Metallaphotoredox catalysis merging photocatalysis and transition metal catalysis is now the most efficient platform for sp3 C–H functionalizations due to its very efficient activation and transformation capability. In such a process, photocatalysis is usually in charge of C–H bond activation to generate an sp3-hybridized carbon-centred radical, whereas transition metal catalysis is in charge of the subsequent transformation of this radical. Here we review advances in sp3 C–H functionalizations under matallaphotoredox catalysis via photocatalytic single-electron transfer mechanisms as opposed to hydrogen atom transfer processes. The delineation of these advancements is initially organized according to distinct sp3 C–H bonds and subsequently categorized by various transition metal catalytic systems. We encompass a thorough exploration of diverse metallaphotoredox catalysis strategies, along with their synthetic applications and mechanisms. Similarities and differences between these strategies are described to inspire new reaction designs, thus promoting further development of this field. The merger of photocatalysis and transition metal catalysis has broadened the scope of chemical reactivity in organic synthesis. This Review provides an overview of the use of metallaphotoredox catalysis for sp3 C–H functionalizations that occur via single-electron, rather than hydrogen atom transfer.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"963-976"},"PeriodicalIF":42.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313979","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