Nature Catalysis最新文献

Selective electroreduction of acetylene to 1,3-butadiene on iodide-induced Cuδ+–Cu0 sites 在碘化物诱导的 Cuδ+-Cu0 位点上将乙炔选择性电还原为 1,3-丁二烯

IF 37.8 1区化学

Nature Catalysis Pub Date : 2024-11-15 DOI: 10.1038/s41929-024-01250-0

Wei Jie Teh, Eleonora Romeo, Shibo Xi, Ben Rowley, Francesc Illas, Federico Calle-Vallejo, Boon Siang Yeo

{"title":"Selective electroreduction of acetylene to 1,3-butadiene on iodide-induced Cuδ+–Cu0 sites","authors":"Wei Jie Teh, Eleonora Romeo, Shibo Xi, Ben Rowley, Francesc Illas, Federico Calle-Vallejo, Boon Siang Yeo","doi":"10.1038/s41929-024-01250-0","DOIUrl":"https://doi.org/10.1038/s41929-024-01250-0","url":null,"abstract":"A crucial task towards creating a sustainable chemical industry is the electrification of chemical processes that produce value-added molecules. One such molecule is 1,3-butadiene (1,3-BD), the feedstock used for manufacturing synthetic rubber. 1,3-BD is traditionally derived, as a by-product, during the energy-intensive steam cracking of naphtha to ethylene. Here we introduce an alternative approach to selectively produce 1,3-BD from the electroreduction of acetylene (e-C2H2R). By using a potassium iodide electrolyte, we created Cuδ+–Cu0 sites on a Cu2O-nanocube-derived catalyst, which are efficacious for promoting e-C2H2R to 1,3-BD. 1,3-BD was formed with a Faradaic efficiency reaching 93% at −0.85 V versus standard hydrogen electrode (SHE) and a partial current density of −75 mA cm−2 at −1.0 V versus SHE. Density functional theory calculations show that I− preserves Cuδ+–Cu0 sites, which facilitate the favourable binding of acetylene, leading to 1,3-BD formation through the coupling of *C2H3 moieties.<figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"246 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637210","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

Photoelectrochemical asymmetric dehydrogenative [2 + 2] cycloaddition between C–C single and double bonds via the activation of two C(sp3)–H bonds 光电化学不对称脱氢[2 + 2] 通过激活两个C（sp3）–H键在C–C单键和双键之间进行环加成

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-11-06 DOI: 10.1038/s41929-023-01050-y

Peng Xiong, Sergei I. Ivlev, Eric Meggers

{"title":"Photoelectrochemical asymmetric dehydrogenative [2 + 2] cycloaddition between C–C single and double bonds via the activation of two C(sp3)–H bonds","authors":"Peng Xiong, Sergei I. Ivlev, Eric Meggers","doi":"10.1038/s41929-023-01050-y","DOIUrl":"10.1038/s41929-023-01050-y","url":null,"abstract":"The efficient generation of high structural complexity, which correlates with the number of stereocentres, is an important objective in organic synthesis. Ideally, from a perspective of economy and sustainability, the conversion should include the direct functionalization of unactivated C(sp3)–H bonds. Here we introduce a methodology that enables the generation of complex cyclobutanes with up to four consecutive stereocentres, including all-carbon quaternary stereocentres, from a direct reaction of C–C single bonds with C=C double bonds. The asymmetric photoelectrocatalysis combines photocatalysis, electrochemical redox catalysis and asymmetric catalysis. It avoids the use of chemical oxidants, exhibits excellent enantioselectivity and diastereoselectivity, reveals high functional group compatibility, and also succeeds in the simultaneous conversion of two C(sp3)–H bonds into consecutive carbon stereocentres. This work demonstrates the power of combining electrochemistry with photochemistry and asymmetric catalysis to generate complex structures in an economic and sustainable fashion. Asymmetric catalytic photoelectrochemical reactions for the construction of complex compounds are underdeveloped. Now, merging photoelectrochemistry with asymmetric catalysis has enabled the dehydrogenative [2 + 2] photocycloaddition between alkyl ketones and alkenes affording enantioenriched cyclobutanes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 12","pages":"1186-1193"},"PeriodicalIF":37.8,"publicationDate":"2023-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71512321","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: 2

Product analogue binding identifies the copper active site of particulate methane monooxygenase 产物类似物结合鉴定颗粒甲烷单加氧酶的铜活性位点

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-11-06 DOI: 10.1038/s41929-023-01051-x

Frank J. Tucci, Richard J. Jodts, Brian M. Hoffman, Amy C. Rosenzweig

{"title":"Product analogue binding identifies the copper active site of particulate methane monooxygenase","authors":"Frank J. Tucci, Richard J. Jodts, Brian M. Hoffman, Amy C. Rosenzweig","doi":"10.1038/s41929-023-01051-x","DOIUrl":"10.1038/s41929-023-01051-x","url":null,"abstract":"Nature’s primary methane-oxidizing enzyme, the membrane-bound particulate methane monooxygenase (pMMO), catalyses the oxidation of methane to methanol. Copper is required for pMMO activity, and decades of structural and spectroscopic studies have sought to identify the active site among three candidates: the CuB, CuC and CuD sites. Challenges associated with the isolation of active pMMO hindered identification of its catalytic centre; however, we have recently shown that reconstituting pMMO into native lipid nanodiscs stabilizes its structure and restores its activity. Here, such active samples were incubated with 2,2,2-trifluoroethanol, a product analogue that serves as a readily visualized active-site probe. Interactions between 2,2,2-trifluoroethanol and the CuD site were observed with pulsed electron nuclear double resonance spectroscopy and cryoelectron microscopy, implicating CuD and the surrounding hydrophobic pocket as the likely site of methane oxidation. Use of these orthogonal techniques on parallel samples is a powerful approach that can circumvent difficulties in interpreting metalloenzyme cryoelectron microscopy maps. Different locations have been proposed for the catalytic centre of particulate methane monooxygenase for methane oxidation to methanol. Now, cryoelectron microscopy structures and electron nuclear double resonance spectroscopic measurements of the enzyme with a product analogue identify CuD as the active site and provide insights into substrate binding.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 12","pages":"1194-1204"},"PeriodicalIF":37.8,"publicationDate":"2023-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71512320","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

H2-reduced phosphomolybdate promotes room-temperature aerobic oxidation of methane to methanol H2还原磷钼酸盐促进甲烷室温好氧氧化制甲醇

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-31 DOI: 10.1038/s41929-023-01011-5

Sikai Wang, Victor Fung, Max J. Hülsey, Xiaocong Liang, Zhiyang Yu, Jinquan Chang, Andrea Folli, Richard J. Lewis, Graham J. Hutchings, Qian He, Ning Yan

{"title":"H2-reduced phosphomolybdate promotes room-temperature aerobic oxidation of methane to methanol","authors":"Sikai Wang, Victor Fung, Max J. Hülsey, Xiaocong Liang, Zhiyang Yu, Jinquan Chang, Andrea Folli, Richard J. Lewis, Graham J. Hutchings, Qian He, Ning Yan","doi":"10.1038/s41929-023-01011-5","DOIUrl":"10.1038/s41929-023-01011-5","url":null,"abstract":"The selective partial oxidation of methane to methanol using molecular oxygen (O2) represents a long-standing challenge, inspiring extensive study for many decades. However, considerable challenges still prevent low-temperature methane activation via the aerobic route. Here we report a precipitated Pd-containing phosphomolybdate, which, after activation by molecular hydrogen (H2), converts methane and O2 almost exclusively to methanol at room temperature. The highest activity reaches 67.4 μmol gcat−1 h−1. Pd enables rapid H2 activation and H spillover to phosphomolybdate for Mo reduction, while facile O2 activation and subsequent methane activation occur on the reduced phosphomolybdate sites. Continuous production of methanol from methane was also achieved by concurrently introducing H2, O2 and methane into the system, where H2 assists in maintaining a moderately reduced state of phosphomolybdate. This work reveals the underexplored potential of such a Mo-based catalyst for aerobic methane oxidation and highlights the importance of regulating the chemical valence state to construct methane active sites. The partial oxidation of methane to methanol is a very attractive yet challenging process. Now, a H2-reduced Pd-containing phosphomolybdate catalyst is reported to convert methane and O2 to methanol with nearly 100% selectivity at room temperature.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 10","pages":"895-905"},"PeriodicalIF":37.8,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49644909","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

Promoting Cu-catalysed CO2 electroreduction to multicarbon products by tuning the activity of H2O 通过调节水的活性促进cu催化CO2电还原成多碳产物

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-31 DOI: 10.1038/s41929-023-01010-6

Hao Zhang, Jiaxin Gao, David Raciti, Anthony Shoji Hall

{"title":"Promoting Cu-catalysed CO2 electroreduction to multicarbon products by tuning the activity of H2O","authors":"Hao Zhang, Jiaxin Gao, David Raciti, Anthony Shoji Hall","doi":"10.1038/s41929-023-01010-6","DOIUrl":"10.1038/s41929-023-01010-6","url":null,"abstract":"The electrochemical reduction of CO2 to valuable C2+ feedstocks is hindered by the competitive formation of C1 products and H2 evolution. Here we tuned the H2O thermodynamic activity between 0.97 and 0.47 using water-in-salt electrolytes to obtain mechanistic insights into the role of H2O in controlling C–C coupling versus C1 product formation on Cu electrodes. By lowering the thermodynamic H2O activity to 0.66, we obtained a Faradaic efficiency of ~73% at a partial current density of −110 mA cm−2 for C2+ products, at modest overpotentials. The adjustment of the thermodynamic H2O activity provided fine control over C2+/C1 ratios, spanning a range from 1 to 20. The trends support the pivotal role of the thermodynamic H2O activity in increasing the CO surface coverages and promoting C–C coupling to C2 products. These findings highlight the potential of tuning thermodynamic H2O activity as a guiding principle to maximize CO2 reduction into highly desirable C2+ products. Copper-based electrocatalysts promote the formation of high-value multicarbon products from CO2, but the process competes with C1 product formation. Now a strategy is presented to tune the activity of water by using water-in-salt electrolytes to increase the C2+/C1 ratio.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 9","pages":"807-817"},"PeriodicalIF":37.8,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46357134","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

Synergistic interactions between PtRu catalyst and nitrogen-doped carbon support boost hydrogen oxidation PtRu催化剂与氮掺杂碳载体的协同作用促进氢氧化

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-31 DOI: 10.1038/s41929-023-01007-1

Weiyan Ni, Josephine Lederballe Meibom, Noor Ul Hassan, Miyeon Chang, You-Chiuan Chu, Anna Krammer, Songlan Sun, Yiwei Zheng, Lichen Bai, Wenchao Ma, Seunghwa Lee, Seongmin Jin, Jeremy S. Luterbacher, Andreas Schüler, Hao Ming Chen, William E. Mustain, Xile Hu

{"title":"Synergistic interactions between PtRu catalyst and nitrogen-doped carbon support boost hydrogen oxidation","authors":"Weiyan Ni, Josephine Lederballe Meibom, Noor Ul Hassan, Miyeon Chang, You-Chiuan Chu, Anna Krammer, Songlan Sun, Yiwei Zheng, Lichen Bai, Wenchao Ma, Seunghwa Lee, Seongmin Jin, Jeremy S. Luterbacher, Andreas Schüler, Hao Ming Chen, William E. Mustain, Xile Hu","doi":"10.1038/s41929-023-01007-1","DOIUrl":"10.1038/s41929-023-01007-1","url":null,"abstract":"Hydroxide exchange membrane fuel cell (HEMFC) is a potentially cost-effective energy conversion technology. However, current state-of-the-art HEMFCs require a high loading of platinum-group-metal (PGM) catalysts, especially for the hydrogen oxidation reaction. Here we develop a porous nitrogen-doped carbon-suppported PtRu hydrogen oxidation reaction catalyst (PtRu/pN-C) that has a high intrinsic and mass activity in alkaline condition. Spectroscopic and microscopic data indicate the presence of Pt single atoms in addition to PtRu nanoparticles on pN-C. Mechanistic study suggests Ru modulates the electronic structure of Pt for an optimized hydrogen binding energy, while Pt single atoms on pN-C optimize the interfacial water structure. These synergetic interactions are responsible for the high catalytic activity of this catalyst. An HEMFC with a low loading of this catalyst and a commercial Fe–N–C oxygen reduction reaction catalyst achieves a high PGM utilization rate. The current density at 0.65 V of this HEMFC reaches 1.5 A cm−2, exceeding the US Department of Energy 2022 target (1 A cm−2) by 50%. Hydroxide exchange membrane fuel cells are promising devices for energy conversion. Now, a porous nitrogen-doped carbon-supported PtRu catalyst for the hydrogen oxidation reaction is presented, consisting of Pt single atoms and PtRu nanoparticles that work synergistically. The catalyst enables a fuel cell that exceeds the US Department of Energy 2022 performance target.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 9","pages":"773-783"},"PeriodicalIF":37.8,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48120235","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

The catalytic role of glutathione transferases in heterologous anthocyanin biosynthesis 谷胱甘肽转移酶在异源花青素生物合成中的催化作用

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-31 DOI: 10.1038/s41929-023-01018-y

Michael Eichenberger, Thomas Schwander, Sean Hüppi, Jan Kreuzer, Peer R. E. Mittl, Francesca Peccati, Gonzalo Jiménez-Osés, Michael Naesby, Rebecca M. Buller

{"title":"The catalytic role of glutathione transferases in heterologous anthocyanin biosynthesis","authors":"Michael Eichenberger, Thomas Schwander, Sean Hüppi, Jan Kreuzer, Peer R. E. Mittl, Francesca Peccati, Gonzalo Jiménez-Osés, Michael Naesby, Rebecca M. Buller","doi":"10.1038/s41929-023-01018-y","DOIUrl":"10.1038/s41929-023-01018-y","url":null,"abstract":"Anthocyanins are ubiquitous plant pigments used in a variety of technological applications. Yet, after over a century of research, the penultimate biosynthetic step to anthocyanidins attributed to the action of leucoanthocyanidin dioxygenase has never been efficiently reconstituted outside plants, preventing the construction of heterologous cell factories. Through biochemical and structural analysis, here we show that anthocyanin-related glutathione transferases, currently implicated only in anthocyanin transport, catalyse an essential dehydration of the leucoanthocyanidin dioxygenase product, flavan-3,3,4-triol, to generate cyanidin. Building on this knowledge, introduction of anthocyanin-related glutathione transferases into a heterologous biosynthetic pathway in baker’s yeast results in >35-fold increased anthocyanin production. In addition to unravelling the long-elusive anthocyanin biosynthesis, our findings pave the way for the colourants’ heterologous microbial production and could impact the breeding of industrial and ornamental plants. Anthocyanins are used in the food and cosmetic industries. Due to the insufficient production in alternative hosts, they are still isolated from plants. Now, this study suggests an important catalytic role of glutathione transferases for the efficient biosynthesis of these natural products.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 10","pages":"927-938"},"PeriodicalIF":37.8,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10593608/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44608598","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

Atomic metal–non-metal catalytic pair drives efficient hydrogen oxidation catalysis in fuel cells 金属-非金属原子催化对驱动燃料电池中高效的氢氧化催化

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-31 DOI: 10.1038/s41929-023-01017-z

Qilun Wang, Huawei Wang, Hao Cao, Ching-Wei Tung, Wei Liu, Sung-Fu Hung, Weijue Wang, Chun Zhu, Zihou Zhang, Weizheng Cai, Yaqi Cheng, Hua Bing Tao, Hao Ming Chen, Yang-Gang Wang, Yujing Li, Hong Bin Yang, Yanqiang Huang, Jun Li, Bin Liu

{"title":"Atomic metal–non-metal catalytic pair drives efficient hydrogen oxidation catalysis in fuel cells","authors":"Qilun Wang, Huawei Wang, Hao Cao, Ching-Wei Tung, Wei Liu, Sung-Fu Hung, Weijue Wang, Chun Zhu, Zihou Zhang, Weizheng Cai, Yaqi Cheng, Hua Bing Tao, Hao Ming Chen, Yang-Gang Wang, Yujing Li, Hong Bin Yang, Yanqiang Huang, Jun Li, Bin Liu","doi":"10.1038/s41929-023-01017-z","DOIUrl":"10.1038/s41929-023-01017-z","url":null,"abstract":"Rational design of efficient hydrogen oxidation reaction (HOR) electrocatalysts with maximum utilization of platinum-group metal sites is critical to hydrogen fuel cells, but remains a major challenge due to the formidable potential-dependent energy barrier for hydrogen intermediate (H*) desorption on single metal centres. Here we report atomically dispersed iridium–phosphorus (Ir–P) catalytic pairs with strong electronic coupling that integratively facilitate HOR kinetics, in which the reactive hydroxyl species adsorbed on the more oxophilic P site induces an alternative thermodynamic pathway to facilely combine with H* on the adjacent Ir atom, whereas isolated single-atom Ir catalysts are inactive. In H2–O2 fuel cells, this catalyst enables a peak power density of 1.93 W cm−2 and an anodic mass activity as high as 17.11 A mgIr−1 at 0.9 ViR-free, significantly outperforming commercial Pt/C. This work not only advances the development of anodic catalysts for fuel cells, but also provides a precise and universal active-site design principle for multi-intermediate catalysis. Fuel cells rely on costly and scarce platinum-group metals to catalyse both anodic and cathodic reactions. Here a catalyst consisting of atomically dispersed iridium and phosphorus on carbon is presented, where adjacent iridium and phosphorus sites work as integrative catalytic pairs to synergically boost the performance for the hydrogen oxidation reaction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 10","pages":"916-926"},"PeriodicalIF":37.8,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46363472","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

Reactant-induced dynamics of lithium imide surfaces during the ammonia decomposition process 氨分解过程中亚胺锂表面的反应物诱导动力学

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-28 DOI: 10.1038/s41929-023-01006-2

Manyi Yang, Umberto Raucci, Michele Parrinello

引用次数: 0

Intramolecular hydroamidation of alkenes enabling asymmetric synthesis of β-lactams via transposed NiH catalysis 烯的分子内氢酰胺化，通过转位NiH催化实现β-内酰胺的不对称合成

IF 37.8 1区化学

Nature Catalysis Pub Date : 2023-08-24 DOI: 10.1038/s41929-023-01014-2

Xiang Lyu, Changhyeon Seo, Hoimin Jung, Teresa Faber, Dongwook Kim, Sangwon Seo, Sukbok Chang

{"title":"Intramolecular hydroamidation of alkenes enabling asymmetric synthesis of β-lactams via transposed NiH catalysis","authors":"Xiang Lyu, Changhyeon Seo, Hoimin Jung, Teresa Faber, Dongwook Kim, Sangwon Seo, Sukbok Chang","doi":"10.1038/s41929-023-01014-2","DOIUrl":"10.1038/s41929-023-01014-2","url":null,"abstract":"Synthetic methods for constructing enantioenriched β-lactams are highly valuable given their ubiquity in bioactive compounds, most notably in antibiotics such as penicillins and carbapenems. Intramolecular hydroamidation of β,γ-unsaturated amides would provide a convenient means to reach this alluring chemical space, yet it remains limited due to the regioselectivity issue arising from the difficulty associated with the formation of strained four-membered rings. Here we describe a NiH-catalysed strategy that addresses this challenge through the use of readily accessible alkenyl dioxazolone derivatives. The reaction transcends the conventional NiH operation mode via a transposed mechanism initiated by N-activation, thus allowing for proximal C–N bond formation with excellent regioselectivity, regardless of the electronic properties of substituents. This mechanistic platform is also highly effective for the enantioselective intramolecular hydroamidation of alkenes to enable a convenient access to enantioenriched β-lactams. Strategies for the asymmetric synthesis of β-lactams are highly sought after. Now, a NiH-catalysed enantioselective intramolecular hydroamidation of alkenes affording β-lactam scaffolds is described, whereby the C–N bond is formed with unusual regioselectivity at the more proximal position.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"6 9","pages":"784-795"},"PeriodicalIF":37.8,"publicationDate":"2023-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44160024","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