Nature Catalysis最新文献_第2页

Achieving mono-selective palladium(II)-catalysed C–H activation of arenes with protein ligands 实现单选择性钯（II）催化芳烃与蛋白质配体的碳氢活化

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-09-08 DOI: 10.1038/s41929-025-01407-5

Hua-Jin Xu, Zhoulong Fan, Bin-Bin Nian, Chen-Hao Gu, Shuo-Jie Shen, Wei Zhang, Yi Hu, Jin-Quan Yu

{"title":"Achieving mono-selective palladium(II)-catalysed C–H activation of arenes with protein ligands","authors":"Hua-Jin Xu, Zhoulong Fan, Bin-Bin Nian, Chen-Hao Gu, Shuo-Jie Shen, Wei Zhang, Yi Hu, Jin-Quan Yu","doi":"10.1038/s41929-025-01407-5","DOIUrl":"10.1038/s41929-025-01407-5","url":null,"abstract":"Achieving mono-selectivity in C–H activation reactions is a considerable challenge when multiple identical C–H bonds coexist. Despite recent rapid advances in site-selective and enantioselective C–H activation, a large number of C–H activation reactions still suffer from poor mono-selectivity. Here we report the use of commercial enzymes as ligands for palladium catalysts, enabling enhanced reactivity and exceptionally high mono-selectivity (up to 99%) in both ortho- and meta-C–H activation of arenes, which originally used bifunctional mono-N-protected amino acid ligands but with poor mono-selectivity. Notably, the Pd–enzyme complex was identified as the active catalyst species. Mechanistic investigations and structural analyses of the enzymes suggest that the enzyme primary structure, the sequence length and the percentage of amino acids with hydrophobic side chains are critical for achieving mono-selectivity. By leveraging these findings, we further developed a glycine-containing oligopeptide capable of achieving similarly high mono-selectivity. Molecular organometallic catalysts typically struggle to activate only one of two identical C–H bonds in arenes for mono-selective C–H activation. Now mono-selectivity has been achieved for Pd(II)-catalysed ortho- or meta-C–H activations using commercial proteins or designed peptides as ligands.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"948-956"},"PeriodicalIF":44.6,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009014","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

Microenvironment effects in electrochemical CO2 reduction from first-principles multiscale modelling 电化学CO2还原中的微环境效应：第一原理多尺度模拟

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-09-08 DOI: 10.1038/s41929-025-01399-2

Francesca Lorenzutti, Ranga Rohit Seemakurthi, Evan F. Johnson, Santiago Morandi, Pavle Nikačević, Núria López, Sophia Haussener

{"title":"Microenvironment effects in electrochemical CO2 reduction from first-principles multiscale modelling","authors":"Francesca Lorenzutti, Ranga Rohit Seemakurthi, Evan F. Johnson, Santiago Morandi, Pavle Nikačević, Núria López, Sophia Haussener","doi":"10.1038/s41929-025-01399-2","DOIUrl":"10.1038/s41929-025-01399-2","url":null,"abstract":"Electrochemical CO2 reduction is expected to become a key player in net-zero technologies, yet its industrial implementation is currently limited. Improvements based on fine-tuning microenvironments (that is, electrolyte environments around catalytic sites) have been scarce due to the interplay between electrode kinetics and transport. Here we couple atomistic insights with continuum transport via ab initio multiscale modelling, explicitly including electrolyte effects at all scales. The resulting model is validated on silver planar electrodes in several liquid electrolytes, and the current dependence with voltage aligns with experimental observations. We show that a balance between CO2 diffusion and cation accumulation needs to be achieved to obtain optimal rates. In ionomers, this limitation can be overcome since organic cation-based microenvironments are present at a fixed concentration, but water management becomes critical. Our approach paves the way towards rational microenvironment design in electrochemical CO2 conversion. Optimizing devices for electrochemical CO2 reduction requires a comprehensive and quantitative understanding of the microenvironments where the reactions occur. Now, a multiscale modelling approach that explicitly accounts for electrolyte effects at all scales is developed and showcased for the electroreduction of CO2 on silver.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"905-918"},"PeriodicalIF":44.6,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009012","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

Enantioselective radical α-enolation of esters via electrochemical chiral isothiourea catalysis 电化学手性异硫脲催化对映选择性自由基α-烯醇化酯

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-09-08 DOI: 10.1038/s41929-025-01408-4

Ning Li, Xuzhen Ye, Yong Liu, Jin Song

{"title":"Enantioselective radical α-enolation of esters via electrochemical chiral isothiourea catalysis","authors":"Ning Li, Xuzhen Ye, Yong Liu, Jin Song","doi":"10.1038/s41929-025-01408-4","DOIUrl":"10.1038/s41929-025-01408-4","url":null,"abstract":"Carboxylic ester motifs are prevalent in biological, chemical and materials sciences, and the asymmetric α-functionalization of simple esters plays a crucial role in the field of organic synthesis. Here we present a versatile electricity-driven asymmetric Lewis base catalysis strategy for the oxidative radical cross-coupling of simple esters with silyl enol ethers. This approach integrates the electrochemical anodic oxidation process with chiral isothiourea catalysis, enabling a polarity inversion at the nucleophilic carbon of the enolate to trigger the formation of a chiral isothiourea-bound α-carbonyl radical species from a C1-ammonium enolate. The combination of asymmetric Lewis base catalysis and electrochemistry unlocks mild oxidative radical coupling reactions, achieving up to 98% enantiomeric excess and demonstrating broad substrate compatibility. This work underscores the synthetic potential of the approach and provides a platform for advancing asymmetric electrosynthesis. Strategies for asymmetric control in electrosynthesis involving radicals are sought after. Now asymmetric Lewis base catalysis is combined with electrochemistry, enabling the oxidative radical cross-coupling of esters with silyl enol ethers and affording γ-keto esters in high enantiomeric excess.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"957-967"},"PeriodicalIF":44.6,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009011","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

A modular synthesis of azetidines from reactive triplet imine intermediates using an intermolecular aza Paternò–Büchi reaction 用分子间aza Paternò-Büchi反应从反应性三态亚胺中间体合成氮杂啶的模块化方法

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-09-05 DOI: 10.1038/s41929-025-01405-7

Benedict A. Williams, Michael J. Tilby, Nicholas A. Parker, Mycah R. Uehling, J. Caleb Hethcox, Dipannita Kalyani, Michael C. Willis

{"title":"A modular synthesis of azetidines from reactive triplet imine intermediates using an intermolecular aza Paternò–Büchi reaction","authors":"Benedict A. Williams, Michael J. Tilby, Nicholas A. Parker, Mycah R. Uehling, J. Caleb Hethcox, Dipannita Kalyani, Michael C. Willis","doi":"10.1038/s41929-025-01405-7","DOIUrl":"10.1038/s41929-025-01405-7","url":null,"abstract":"Azetidines are four-membered saturated N-heterocycles that are of interest in discovery chemistry. However, the implementation of these structures is limited by their synthetic intractability, resulting from their inherent ring strain. An approach that circumvents this is the intermolecular [2 + 2] photocycloaddition between imines and alkenes. However, this is unworkable with simple acyclic imines and non-activated alkenes, due to the inability to generate suitably reactive imine-derived triplet intermediates. Here we show that simple acyclic imines bearing N-sulfamoyl fluoride substituents generate reactive triplet imines that react with a broad range of alkenes to produce azetidine products in high yields. Mechanistic and computational studies confirm the key role of the sulfamoyl fluoride unit in dictating the [2 + 2] pathway. In addition, the sulfamoyl fluoride substituents offer a convenient reaction site for product functionalization or for traceless removal. The advent of synthetically useful imine-derived triplets should initiate further research and applications of these elusive reactive intermediates. Azetidines are four-membered saturated N-heterocycles that are of interest in drug discovery and medicinal chemistry. Here the authors report how sulfamoyl fluoride substituents tune the reactivity of acyclic imine-derived triplet intermediates for the synthesis of azetidines via a [2 + 2] photocycloaddition reaction with alkenes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"939-947"},"PeriodicalIF":44.6,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01405-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144995650","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

Site-selective Ru-catalysed saturation of unactivated arenes via directed 6π activation 通过定向6π活化，钌催化非活化芳烃的选择性饱和

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-08-28 DOI: 10.1038/s41929-025-01404-8

Congjun Yu, Linda Yiu, Zining Zhang, Guangbin Dong

{"title":"Site-selective Ru-catalysed saturation of unactivated arenes via directed 6π activation","authors":"Congjun Yu, Linda Yiu, Zining Zhang, Guangbin Dong","doi":"10.1038/s41929-025-01404-8","DOIUrl":"10.1038/s41929-025-01404-8","url":null,"abstract":"Directing group-based strategies have proven highly effective for site-selective functionalization of π bonds in alkenes and carbonyls, as well as C–H and C–C bonds, but have yet to be demonstrated for unactivated aromatic π-systems. Meanwhile, catalytic hydrogenation of arenes to their corresponding saturated carbo- or heterocycles offers a straightforward approach to increase molecular three-dimensionality and sp3 carbon content in pharmaceutical compounds; however, it remains challenging to achieve site-selective dearomatization among electronically and sterically unbiased arenes. Here we report a Ru-catalysed directed arene saturation, which selectively reduces the aryl group adjacent to the directing moiety. Remarkably, a number of easily reducible functional groups are compatible with the mild reaction conditions. The preliminary mechanistic study reveals a homogeneous catalysis process and the potential involvement of an η6-arene-ruthenium intermediate. The synthetic utility of this method is demonstrated in the streamlined synthesis of cis-atovaquone, gram-scale reactions and late-stage saturation of complex bioactive compounds. Directing group strategies for selective dearomatization of unactivated aromatic π-systems have remained elusive. Now a homogeneous ruthenium catalyst, aided by a removable directing group, enables the site-selective hydrogenation of less reactive arene moieties in polyaryl compounds.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"931-938"},"PeriodicalIF":44.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910713","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

Copper-catalysed enantioconvergent O-alkylation of alcohols with racemic α-tertiary haloamides to access enantioenriched hindered dialkyl ethers 铜催化醇与外消旋α-叔卤酰胺的对映收敛o -烷基化反应得到富集对映体的受阻二烷基醚

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-08-28 DOI: 10.1038/s41929-025-01402-w

Jia-Yong Zhang, Ji-Jun Chen, Boming Shen, Jia-Heng Fang, Xuan-Yi Du, Ning-Yuan Yang, Chang-Jiang Yang, Wei-Long Liu, Fu Liu, Zhong-Liang Li, Qiang-Shuai Gu, Zhe Dong, Peiyuan Yu, Xin-Yuan Liu

{"title":"Copper-catalysed enantioconvergent O-alkylation of alcohols with racemic α-tertiary haloamides to access enantioenriched hindered dialkyl ethers","authors":"Jia-Yong Zhang, Ji-Jun Chen, Boming Shen, Jia-Heng Fang, Xuan-Yi Du, Ning-Yuan Yang, Chang-Jiang Yang, Wei-Long Liu, Fu Liu, Zhong-Liang Li, Qiang-Shuai Gu, Zhe Dong, Peiyuan Yu, Xin-Yuan Liu","doi":"10.1038/s41929-025-01402-w","DOIUrl":"10.1038/s41929-025-01402-w","url":null,"abstract":"The cross-coupling of bulky electrophiles and nucleophiles to form sterically congested molecules is a challenging issue in modern synthetic chemistry. Among them, chiral hindered dialkyl ethers are one class of valuable motifs, but the catalytic asymmetric synthesis of such motifs from readily available tertiary alcohols and racemic electrophiles remains underexplored. Challenges arise from the steric hindrance of both reactants, the difficulty in enantiodiscriminating the three substituents of tertiary electrophiles and the low nucleophilicity of bulky alcohols. Here we show the copper-catalysed enantioconvergent radical O-alkylation of diverse alcohols with racemic α-tertiary haloamides to access enantioenriched hindered dialkyl ethers. Successful realization of this strategy relies on the development of anionic N,N,N-ligands with a side arm to form coordinatively saturated key Cu(iii) intermediates, therefore exerting remarkable chemo- and enantioselectivity. The synthetic potential is showcased by the late-stage functionalization and stereodivergent synthesis of four stereoisomers of a product with two stereocentres. The O-alkylation of tertiary alcohols with racemic tertiary electrophiles to access chiral hindered dialkyl ethers has remained elusive. Now this synthetic challenge has been accomplished by copper-catalysed C–O cross-coupling between tertiary haloamides and alcohols using designed ligands.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"919-930"},"PeriodicalIF":44.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910716","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

Electrocatalytic upcycling of high-pressure captured CO2 to ethylene 高压捕集二氧化碳电催化升级回收制乙烯

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-08-28 DOI: 10.1038/s41929-025-01411-9

Liang Huang, Ge Gao, Jiwu Zhao, William L. Roberts, Xu Lu

{"title":"Electrocatalytic upcycling of high-pressure captured CO2 to ethylene","authors":"Liang Huang, Ge Gao, Jiwu Zhao, William L. Roberts, Xu Lu","doi":"10.1038/s41929-025-01411-9","DOIUrl":"10.1038/s41929-025-01411-9","url":null,"abstract":"Electrochemical upcycling of captured CO2 under high pressure holds significant potential to bridge between CO2 emissions and hydrocarbon commodities, yet it remains underexplored. Here we convert gas-phase high-pressure captured CO2 into ethylene (C2H4) using a high-pressure membrane electrode assembly equipped with In/Cu catalysts, affording up to 85% Faradaic efficiency and 750 mA cm−2 partial current density under 20 bar. Theoretical calculations and operando studies link enhanced C–C coupling to the pressure-modulated *CO adsorption configuration and elevated CO2 coverage. High pressure also mitigates salt precipitation by relocating bicarbonate formation to the catalyst–membrane interface, enabling stable electrolysis for over 1,500 h at 600 mA cm−2. As a proof of concept, by recapturing residual CO2, the system delivers industrial-grade 99.9% purity C2H4, creating an opportunity to turn the otherwise costly CO2 capture into a profit. Energy analysis suggests that directly valorizing high-pressure captured CO2, instead of depressurizing and repressurizing, is essential to minimize energy consumption. Electrocatalytic CO2 conversion offers opportunities for producing sustainable fuels and chemicals, but achieving strong performance with realistic CO2 sources remains a challenge. Here a system is designed to use high-pressure captured CO2, and achieves 85% Faradaic efficiency and high-purity C2H4 for over 1,500 h.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"968-976"},"PeriodicalIF":44.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910714","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

Linking surface modifications of Cu(100) to selectivity during dynamic CO2 electroreduction 动态CO2电还原过程中Cu（100）的表面修饰与选择性的联系

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-08-25 DOI: 10.1038/s41929-025-01403-9

引用次数: 0

Redesigning electrolysers in coupled electrolysis 耦合电解中电解槽的重新设计

IF 44.6 1区化学

Nature Catalysis Pub Date : 2025-08-22 DOI: 10.1038/s41929-025-01384-9

Junting Dong, Chang Yu, Jieshan Qiu

引用次数: 0

Iron–sulfur cluster with double duty 具有双重作用的铁硫簇

IF 44.6 1区化学