Nature Catalysis最新文献

{"title":"Chiral cyclopropanes with light in confined space","authors":"Magdalena Walewska-Królikiewicz, Dorota Gryko","doi":"10.1038/s41929-025-01345-2","DOIUrl":"https://doi.org/10.1038/s41929-025-01345-2","url":null,"abstract":"Several strategies for the enantioselective synthesis of small cyclic alkanes from achiral building blocks are known, but general and sustainable methods still represent a daunting challenge. Now, the cooperation of asymmetric counterion-directed catalysis with photoredox activation complements metalloorganic and enzymatic methods for the synthesis of chiral cyclopropanes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"128 1","pages":"413-414"},"PeriodicalIF":37.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165392","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":"A polyheteroatomic Diels–Alderase","authors":"Jan-Stefan Völler","doi":"10.1038/s41929-025-01351-4","DOIUrl":"https://doi.org/10.1038/s41929-025-01351-4","url":null,"abstract":"<p>Now, Yi-Lei Zhao, Mehdi Mobli and Xudong Qu report a polyheteroatomic Diels–Alderase that catalyses the intramolecular cycloaddition of a C=O diene with a C=O dienophile. The researchers had previously worked on the elucidation of the biosynthesis of the polyketide antibiotic (−)-anthrabenzoxocinone (<b>(−)-ABX</b>). However, the construction of the oxygen-bridged tricyclic acetal of <b>(−)-ABX</b> from phenyldimethylanthrone (<b>1</b>) remained unclear. In the present work, investigations continued with knocking out genes of the biosynthetic gene cluster and analysing the reaction products. The results indicated that <b>1</b> was stereo-specifically reduced by the enzyme Abx₍₋₎E to compound <b>2</b> followed by its subsequent stereo-specific transformation into <b>(−)-ABX</b> by Abx₍₋₎F (pictured). This was confirmed by in vitro studies using the purified enzymes revealing a <i>k</i>_cat/<i>K</i>_M value of 3.43 ± 0.23 min⁻¹ μM⁻¹ for Abx₍₋₎F with <b>2</b>. Mechanistic experiments all pointed to Abx₍₋₎F being a bifunctional enzyme that catalyses the formation of <b>(−)-ABX</b> by dehydration of compound <b>2</b> to a reactive <i>o</i>-quinone methide intermediate <b><i>(Z, Ra)</i></b><b>-3</b> and a subsequent dual-oxa HDA (pictured). Structural insights were gained by nuclear magnetic resonance spectroscopy and by solving the crystal structure of Abx₍₋₎F. This enabled the identification of the active side residues, which were then mutated to probe the reaction mechanism. With this approach Asp17 was found to act as a general base that mediates the dehydration to generate the <i>o</i>-quinone methide intermediate <b><i>(Z, Ra)</i></b><b>-3</b> and residues in the enzyme’s active site were identified that control the stereochemistry in the subsequent dual-oxa HDA.</p><p>This work expands the scope of biocatalytic Diels–Alder reactions and shows the power of enzymes to control reactive intermediates and stereoselectivity. Polyheteroatomic Diels–Alderases hold promise for the sustainable synthesis of complex bioactive molecules, with implications for drug discovery.</p>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"148 1","pages":"409-409"},"PeriodicalIF":37.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165389","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":"Modulation to probe the interface","authors":"Marçal Capdevila-Cortada","doi":"10.1038/s41929-025-01356-z","DOIUrl":"https://doi.org/10.1038/s41929-025-01356-z","url":null,"abstract":"<p>Now, Dimosthenis Sokaras, Junko Yano and colleagues use modulation excitation X-ray absorption spectroscopy to capture copper’s speciation in situ at the electrode–electrolyte interface in a time-resolved manner. This technique tracks the difference in X-ray absorbance at each given incident energy between two applied potentials that are periodically interchanged, thus achieving high sensitivity to those species that respond to the applied potentials, that is, those at the electrode–electrolyte interface; and their kinetics can be extracted too.</p><p>The researchers focus on the Cu K-edge region for two sets of potentials, 0 to 0.5 V versus the reversible hydrogen electrode (V_RHE) and –0.4 to 0.8 V_RHE, in 0.1 M KHCO₃ electrolyte using a polycrystalline Cu electrode. The applied potential conditions simulate those during start-up/shut-down events. The results point to an early oxidation to Cu(I) hydroxide upon switching to the anodic potential, quickly evolving to Cu₂O, with Cu(OH)₂ also forming to a lesser degree, under the 0 to 0.5 V_RHE protocol. On the other hand, the wider potential protocol results in Cu(OH)₂ as the main species, together with some CuO and Cu₂O.</p>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"120 1","pages":"411-411"},"PeriodicalIF":37.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165259","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":"Unlocking iron spin states for oxygen reduction","authors":"Jaehyuk Shim, Yung-Eun Sung","doi":"10.1038/s41929-025-01343-4","DOIUrl":"https://doi.org/10.1038/s41929-025-01343-4","url":null,"abstract":"Iron single-atom catalysts are shown to achieve high oxygen reduction reaction activity by stabilizing a high-spin Fe3+N4 centre, which optimizes intermediate binding and catalytic turnover. This discovery provides crucial insights into how electronic structure dictates performance, guiding the design of non-precious-metal catalysts for sustainable energy conversion technologies.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"49 1","pages":"417-419"},"PeriodicalIF":37.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165393","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":"Ordered single active sites for cascade hydrogenation and hydroformylation reactions","authors":"Xiaojun Lu, Jiazhen Wu, Xinyi He, Zichuang Li, Yangfan Lu, Wenqian Li, Jiang Li, Miao Xu, Yanpeng Qi, Qing Zhang, Yijia Liu, Meng Du, Toshio Kamiya, Hideo Hosono, Fusheng Pan, Jie-Sheng Chen, Tian-Nan Ye","doi":"10.1038/s41929-025-01346-1","DOIUrl":"https://doi.org/10.1038/s41929-025-01346-1","url":null,"abstract":"<p>Metal single-atom catalysts offer improved activity and selectivity due to their unique electronic and coordination properties compared with bulk metals. However, many single-atom catalysts suffer from randomly dispersed active sites and limited electron-donating ability due to bonding with electronegative elements or less reactive metals. Here we demonstrate that Mg-rich intermetallic Mg₂₉TM₄ (TM = Pd, Rh, Ir, Pt) nanocatalysts overcome these limitations. These materials feature periodically dispersed, electron-rich single-atom sites of noble metals within a uniform chemical environment. Mg₂₉TM₄ exhibits high activity and selectivity in C₂H₂ semihydrogenation (Mg₂₉Pd₄) and olefin hydroformylation (Mg₂₉Rh₄), with Mg₂₉Rh₄ achieving high regioselectivity for branched aldehydes (branched:linear &gt; 200:1). Kinetic and density functional theory studies suggest that the Mg–TM ensemble enables precise control over carbon–carbon multiple bond adsorption and activation, enhancing both activity and selectivity. Furthermore, the ternary Mg₂₉Pd_1.3Rh_2.7 catalyst, with its synergistic Mg–Pd and Mg–Rh dual single-atom sites, efficiently catalyses a cascade reaction involving phenylacetylene hydrogenation followed by hydroformylation.</p><figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"591 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137205","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":"SnSe nanosheets with Sn vacancies catalyse H2O2 production from water and oxygen at ambient conditions","authors":"Xinyue Zhang, Yangyang Wan, Yi Wen, Yingcai Zhu, Hong Liu, Jiaxiang Qiu, Zhanpeng Zhu, Zhongti Sun, Xiang Gao, Shulin Bai, Yuqiao Zhang, Long Zhang, Xiaohong Yan, Jianming Zhang, Yong Liu, Shun Li, Li-Dong Zhao","doi":"10.1038/s41929-025-01335-4","DOIUrl":"https://doi.org/10.1038/s41929-025-01335-4","url":null,"abstract":"<p>Hydrogen peroxide (H₂O₂) is a vital industrial chemical and sustainable energy carrier. However, achieving a simple, efficient and cost-effective synthesis under mild conditions remains an important challenge. Here we show that SnSe nanosheets with Sn vacancies can directly catalyse H₂O₂ production from H₂O and O₂ under ambient conditions, without additional energy inputs (for example, light and electricity), cocatalysts or sacrificial reagents. This approach achieves an optimal H₂O₂ production rate of ~2.6 mmol g⁻¹ h⁻¹ at 40 °C and maintains long-term stable production (~0.3 mmol l⁻¹) in a continuous-flow reactor for over 50 h at room temperature. Experimental and theoretical analyses reveal that this unique thermocatalytic effect arises from a dynamic process involving Sn vacancy defect-induced sequential dissociation of H₂O and activation of O₂ molecules, along with reversible surface restructuring of the SnSe nanosheets to release H₂O₂. Our findings offer a notably simple, highly efficient and entirely green strategy for H₂O₂ production, with broader implications in other catalytic reactions involving water activation.</p><figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"140 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122592","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":"Selective formaldehyde condensation on phosphorus-rich copper catalyst to produce liquid C3+ chemicals in electrocatalytic CO2 reduction","authors":"Minjun Choi, Sooan Bae, Yeongin Kim, Youjin Lee, Mokyeon Cho, Sinwoo Kang, Jaeyoung Lee","doi":"10.1038/s41929-025-01341-6","DOIUrl":"https://doi.org/10.1038/s41929-025-01341-6","url":null,"abstract":"<p>Recent advancements in the CO₂ reduction reaction (CO₂RR) target multicarbon chemical production and scalable electrode designs for industrial applications. Here we introduce a zero-gap cell utilizing humidified gas-phase CO₂ and circulated alkaline media, achieving a Faradaic efficiency of 66.9% for C₃₊ products and a current density of −1,100 mA cm⁻². In situ spectroscopic analyses revealed formaldehyde as a key intermediate formed on copper oxide/hydroxide interfaces derived from a phosphorus-rich copper catalyst. Unlike conventional pathways based on dimerization of CO intermediates, our study selectively produces liquid-phase multicarbon products because of autonomous local pH variations under a weak alkaline microenvironment, with allyl alcohol as the dominant C₃₊ product. The high selectivity and efficiency for liquid products provide a substantial advantage for storage and transport, highlighting the scalability and practical feasibility of our approach, which offers a potential economically viable solution for CO₂ utilization. This development encourages the adoption of CO₂RR technologies in iron–steel and petrochemical industries to mitigate greenhouse gas emissions.</p><figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"59 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113527","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":"Cobalt-catalysed alkene hydronitration enabled by anomeric nitroamide","authors":"Yu Wang, Marcell M. Bogner, Jake B. Bailey, Lauren N. Grant, Milan Gembicky, Paul F. Richardson, Phil S. Baran","doi":"10.1038/s41929-025-01336-3","DOIUrl":"https://doi.org/10.1038/s41929-025-01336-3","url":null,"abstract":"<p>Tertiary nitroalkanes, as well as their reduced products, α-tertiary amines, play an essential role in drug discovery as either key synthetic precursors or final motifs in targeted molecules. Existing methods to prepare tertiary nitro compounds generally rely on polar-bond disconnections, in which strong bases or highly active electrophiles are needed. Here we report the development of an anomeric nitroamide-based reagent that enables selective metal-hydride hydrogen atom transfer-based Co-catalysed alkene hydronitration for the preparation of valuable tertiary nitro compounds. This mild, scalable reaction shows broad functional group tolerance. Its synthetic application is demonstrated via late-stage nitration of complex alkenes derived from drugs and natural products, and simplifying the synthesis of a rare naturally occurring nitro sugar. Simple access to isotopically labelled ¹⁵N-containing nitro compounds is also disclosed. The anomeric nitroamide reagent was deemed safe by energetic measurements and its reactivity rationalized based on X-ray crystallographic analysis.</p><figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"56 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104482","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":"Dissolved Fe species enable a cooperative solid–molecular mechanism for the oxygen evolution reaction on NiFe-based catalysts","authors":"Chunguang Kuai, Liping Liu, Anyang Hu, Yan Zhang, Yuxin Zhang, Dawei Xia, Dennis Nordlund, Dimosthenis Sokaras, Donato Decarolis, Diego Gianolio, Hongliang Xin, Luxi Li, Feng Lin","doi":"10.1038/s41929-025-01342-5","DOIUrl":"https://doi.org/10.1038/s41929-025-01342-5","url":null,"abstract":"<p>The oxygen evolution reaction is a key process in many energy technologies, but improving its efficiency remains challenging due to the energy scaling relationships that limit the reaction kinetics on conventional single-active-site solid catalysts. Here we report a cooperative solid–molecular mechanism for oxygen evolution on NiFe-based hydroxide electrocatalysts. By identifying the critical interfacial species and understanding their dynamics, we find that molecular FeO₄²⁻ species, derived from the dissolution of Fe from the solid catalyst, act as molecular co-catalysts that participate in the critical O–O bond-formation step along with solid sites. This synergistic mechanism, involving both solid and molecular active species, circumvents the typical scaling limitations observed for solid catalysts alone. Our findings reveal an unconventional solid–molecular mechanism that governs electrocatalysis at the solid–liquid interface and suggest a strategy for transcending scaling constraints through cooperative multi-site catalysis.</p><figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"41 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144097157","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":"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":"<p>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.</p><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}