Nature Catalysis最新文献

Organocatalytic regio- and stereoselective cyclopropanation of olefins 烯烃的有机催化区域选择性和立体选择性环丙烷化

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-05-16 DOI: 10.1038/s41929-025-01340-7

Chendan Zhu, Sayantani Das, Avishek Guin, Chandra Kanta De, Benjamin List

{"title":"Organocatalytic regio- and stereoselective cyclopropanation of olefins","authors":"Chendan Zhu, Sayantani Das, Avishek Guin, Chandra Kanta De, Benjamin List","doi":"10.1038/s41929-025-01340-7","DOIUrl":"https://doi.org/10.1038/s41929-025-01340-7","url":null,"abstract":"As reactive intermediates and substructures of natural products and bioactive molecules, the smallest cyclic alkanes—cyclopropanes—are an attractive class of molecules for chemists. Arguably, the most general approach to their chemical synthesis involves the addition of metal carbenes to olefins. Whereas catalytic asymmetric cyclopropanations of electronically unbiased olefins with carbenoids have been reported using chiral metal complexes and engineered metalloenzymes, we now report a complementary, metal-free and highly enantioselective cyclopropanation of olefins with diazoalkanes, applying asymmetric counteranion-directed photoredox organocatalysis. We identify an ion pair featuring a thioxanthylium photoredox cation and a chiral imidodiphosphorimidate counteranion that catalyses highly enantioselective cyclopropanations of styrenes and aliphatic dienes with diazo compounds. Mechanistic investigations reveal a wavelength dependence of the enantioselectivity and suggest that the main catalytic pathway proceeds via olefin-derived radical cation intermediates. This metal-free, highly enantioselective organocatalytic approach complements previously reported methods for alkene manipulations.<figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"1 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066183","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

Understanding two voltammetric features of water reduction and water oxidation in mild pH solutions 了解在温和pH溶液中水还原和水氧化的两个伏安特性

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-05-14 DOI: 10.1038/s41929-025-01339-0

Xin Yuan, Michael T. Bender, Myohwa Ko, Kyoung-Shin Choi

引用次数: 0

Asymmetric Hofmann–Löffler–Freytag-type reaction via a transient carbenium ion complex merging organocatalysis and photocatalysis 不对称Hofmann-Löffler-Freytag-type反应通过瞬态碳离子络合物合并有机催化和光催化

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-29 DOI: 10.1038/s41929-025-01329-2

Qihang Guo, Yihui Mao, Jiren Liu, Lujing Zhu, Xin Hong, Zhan Lu

引用次数: 0

Illuminating enantioselective alkyl−alkyl coupling 照亮对映选择性烷基-烷基偶联

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01327-4

Weisai Zu, Xinlong Luo, Haohua Huo

引用次数: 0

Reflecting on interphases 对界面的反思

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01332-7

Benjamin Martindale

{"title":"Reflecting on interphases","authors":"Benjamin Martindale","doi":"10.1038/s41929-025-01332-7","DOIUrl":"https://doi.org/10.1038/s41929-025-01332-7","url":null,"abstract":"The use of neutron reflectometry is crucial since the light elements lithium and hydrogen are practically invisible to more commonly used X-ray techniques. A number of detailed insights about the exchange of species between the SEI and electrolyte are revealed in a series of experiments. First, the identity of the Li salt has a profound impact of the SEI formation with a more well-defined layer observed in LiBF4 than in LiClO4. Specifically, the structure consists of a thick, diffuse outer layer with a thin compact inner layer at low current density and low cycling that merge into a single layer after increased current cycling. Then, the use of isotopically (deuterium) labelled solvent (THF) and proton donor (ethanol) reveals that the proton donor impacts the inner layer while the solvent controls the outer. In the absence of any proton donor, dendritic growth of Li occurred at the expense of Li3N and LiH. Finally, neutron absorption also allowed the observation of boron incorporation into the SEI in the case of LiBF4.These insights contribute towards explaining the previous observations that the selectivity and stability of Li-mediated N2RR are improved by the use of fluorinated electrolytes. More broadly, it exemplifies the need for deepened understanding of SEI evolution and the power of SEI engineering through electrolyte additives.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 1","pages":"284-284"},"PeriodicalIF":37.8,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143875966","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

Revealing hidden nanoscale electrocatalysis 揭示隐藏的纳米级电催化

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01326-5

Steven McIntosh

引用次数: 0

Bridging catalysis 桥接催化

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01338-1

Francesco Zamberlan

{"title":"Bridging catalysis","authors":"Francesco Zamberlan","doi":"10.1038/s41929-025-01338-1","DOIUrl":"https://doi.org/10.1038/s41929-025-01338-1","url":null,"abstract":"The team first analysed a model liquid phase system for this reaction, composed of acetic acetic-potassium acetate solution with Pd/C, and found that Pd(0) is subjected to corrosion by molecular oxygen. This allows the solubilization of the metal as Pd(II) acetate, with the Pd(II) species then reacting with ethylene to yield VA and metallic Pd(0) as precipitate. They also notice that Pd/C promotes the reaction better than bulk Pd. They also found this is valid also for the electrochemical and thermochemical processes of model VA production in the absence of O2: in all cases, the Pd(II) species is solvated from the solid support upon a corrosion event, but the Pd reoxidation is a heterogeneous process upon which Pd(0) particles are dispersed on the support, as confirmed by TEM measurements, ready for the subsequent corrosion step in the next catalytic cycle. Finally, the same electrochemical behaviour is also observed in a model system of the process’ industrial conditions.Surendranath and co-workers’ investigations point to a dynamic interplay between heterogeneous Pd(0) and homogenous Pd(II) species, with a catalytic system that challenges the current catalytic phase separation paradigm, highlighting the intricate relationship between homogeneous and heterogeneous modes of reaction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"16 1","pages":"286-286"},"PeriodicalIF":37.8,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143875964","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 matters 氧气的重要

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01333-6

Marcal Capdevila-Cortada

{"title":"Oxygen matters","authors":"Marcal Capdevila-Cortada","doi":"10.1038/s41929-025-01333-6","DOIUrl":"https://doi.org/10.1038/s41929-025-01333-6","url":null,"abstract":"Now, Chris-Kriton Skylaris and colleagues, in a collaboration between the University of Southampton and Johnson Matthey, study the impact of oxidation effects on Pt nanoparticles (NPs) to the ORR by computational means. To that end, they perform grand canonical minimization Monte Carlo simulations using the recently developed MACE-MP-0 machine learning interatomic potentials, which allows the treatment of the large Pt NPs (Pt353 plus oxygen atoms, up to a total of 896 atoms) with nearly density functional theory accuracy at a fixed chemical potential.The researchers obtain the Pt NP’s most stable oxygen content at each given voltage and derive a volcano plot that associates a rate-determining step and onset overpotential to each oxygen content. These results are thus a consequence of both thermodynamic considerations and site-blocking effects due to the presence of oxide species. The latter effects are studied in detail via a deletion energy analysis, which reveals the heterogeneity of surface oxide species. In addition, a shift in the d-band centre is found with the oxygen content highlighting two distinct regimes, which is related to the formation of an oxide phase at higher oxygen content. Finally, a kinetic model that includes the above considerations is derived.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"31 1","pages":"285-285"},"PeriodicalIF":37.8,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143875965","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

Regioselective silyl installation for arene diversification 芳烃多样化的区域选择性硅基装置

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01314-9

引用次数: 0

Rings for interfacial catalysis 用于界面催化的环

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-25 DOI: 10.1038/s41929-025-01331-8

Jan-Stefan Völler

{"title":"Rings for interfacial catalysis","authors":"Jan-Stefan Völler","doi":"10.1038/s41929-025-01331-8","DOIUrl":"https://doi.org/10.1038/s41929-025-01331-8","url":null,"abstract":"Now, Yilin Wang, Bing Liu and co-workers developed a type of emulsion, where the droplets are covered by a densely packed colloidal SiO2 ring monolayer (pictured). Besides enhancing the stability, the SiO2 rings are hollow so that the liquid–liquid interface of the droplets remains largely accessible, enabling efficient diffusion and operation of the catalysts. First, fluorescent rhodamine B was used to visualize the enhanced diffusion through the interface of water-in-cyclohexane ring-stabilized Pickering emulsion (RPE) compared to conventional nanosphere-stabilized PEs (SPE). Having this beneficial feature confirmed the researchers set out to use it for enhancing catalytic reactions. Lipase was added to the water phase of toluene-in water RPE. The enzyme accumulated at the interface and catalysed the hydrolysis of oil-soluble 4-nitrophenyl palmitate to water-soluble p-nitrophenol, which quickly diffused to the water-phase. This set-up outperformed other conventional emulsion systems in terms of reaction conversion and specific activity of lipase. Then, the authors applied the RPE for the haemoglobin-catalysed oxidation of pyrogallol that not only takes place at the interface but also in in the water phase. RPE again showed significantly faster conversion compared to other PE systems, which was attributed to the faster diffusion of the products from the aqueous phase to the organic phase. Finally, a Pd NP-loaded RPE was generated, and it was shown that it performed better than the corresponding SPE system for the oxidation of benzyl alcohol in batch and continuous flow interfacial catalysis due to higher accumulation of Pd NPs at the interface.Taken together, the researchers have successfully addressed the problem of low interface accessibility of particle-stabilized Pickering emulsions and have convincingly demonstrated the advantages of the developed ring-stabilized system for catalytic applications.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 1","pages":"283-283"},"PeriodicalIF":37.8,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876079","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