Pub Date : 2024-05-29DOI: 10.1038/s41929-024-01163-y
Gina Dotta, Alejandro J. Vila
The understanding of protein evolution is a central challenge in biology. Now, the evolution of a β-lactamase in vitro reveals that the total effect of mutations can change the rate-limiting step of the catalytic mechanism.
{"title":"Order matters in evolution","authors":"Gina Dotta, Alejandro J. Vila","doi":"10.1038/s41929-024-01163-y","DOIUrl":"10.1038/s41929-024-01163-y","url":null,"abstract":"The understanding of protein evolution is a central challenge in biology. Now, the evolution of a β-lactamase in vitro reveals that the total effect of mutations can change the rate-limiting step of the catalytic mechanism.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141177228","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}
Pub Date : 2024-05-29DOI: 10.1038/s41929-024-01164-x
Jan Lukas Krüsemann, Steffen N. Lindner
The future of bioproduction lies in efficient C1 utilization. Methanol derived from CO2 can be fed to engineered bacteria that convert it into platform chemicals currently produced from fossil fuels. Now, recent results confirm we are getting closer.
{"title":"Bioproduction from methanol","authors":"Jan Lukas Krüsemann, Steffen N. Lindner","doi":"10.1038/s41929-024-01164-x","DOIUrl":"10.1038/s41929-024-01164-x","url":null,"abstract":"The future of bioproduction lies in efficient C1 utilization. Methanol derived from CO2 can be fed to engineered bacteria that convert it into platform chemicals currently produced from fossil fuels. Now, recent results confirm we are getting closer.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141177395","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}
Pub Date : 2024-05-29DOI: 10.1038/s41929-024-01144-1
Eric Liu, Drew Higgins
Platinum-free electrocatalysts for anion exchange membrane fuel cells and water electrolysers are required to improve the techno-economic viability of these electrochemical technologies for the sustainable production and use of hydrogen. Modifying the electronic structure of Li-intercalated layered Mn-oxides via Ru doping resulted in a catalyst displaying impressive performance towards both technologies.
{"title":"Tunable layered Mn oxides for oxygen electrocatalysis","authors":"Eric Liu, Drew Higgins","doi":"10.1038/s41929-024-01144-1","DOIUrl":"10.1038/s41929-024-01144-1","url":null,"abstract":"Platinum-free electrocatalysts for anion exchange membrane fuel cells and water electrolysers are required to improve the techno-economic viability of these electrochemical technologies for the sustainable production and use of hydrogen. Modifying the electronic structure of Li-intercalated layered Mn-oxides via Ru doping resulted in a catalyst displaying impressive performance towards both technologies.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141177443","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}
Catalysts with tailored structures are crucial to determine the selectivity of chemical reactions. However, the design of catalyst structures for the selective cleavage of hydroxylic C–O(H) bonds while retaining etheric C–O(R) bonds remains a challenge and needs to be comprehensively explored. Here we report a series of mesoporous-carbon-supported platinum–cobalt (Pt–Co) bimetallic electrocatalysts in which different intermetallic interactions between Pt and Co species result in different hydrodeoxygenation and hydrogenation routes. Notably, Pt nanoparticles decorated with Co single atoms afford the selective cleavage of the C–O(H) bond in guaiacol and other lignin derivatives adjacent to an etheric C–O(R) bond with ether selectivities of >72.1%, and also work extensively for various other substrates with different substituents. This work highlights that a thorough understanding of the structure–performance relationship is crucial to rationally design and construct suitable catalysts with tailored sites for desired catalytic reactions. Being able to selectively derive desired compounds from biomass feedstock is very challenging. Now the selectivity of Pt–Co catalysts for the electroreduction of guaiacol and other lignin-derived substrates is shown to depend on the Co speciation and preferential C–OH cleavage can be obtained, retaining the C–OR group.
具有定制结构的催化剂对于确定化学反应的选择性至关重要。然而，如何设计出既能选择性裂解羟基 C-O(H)键又能保留醚基 C-O(R)键的催化剂结构仍然是一个挑战，需要进行全面的探索。我们在此报告了一系列介孔碳支撑的铂-钴（Pt-Co）双金属电催化剂，其中铂和钴之间不同的金属间相互作用导致了不同的氢脱氧和氢化路线。值得注意的是，用 Co 单原子装饰的铂纳米粒子可选择性地裂解愈创木酚和其他木质素衍生物中邻近醚 C-O(R)键的 C-O(H)键，醚选择性高达 72.1%，而且还可广泛用于具有不同取代基的各种其他底物。这项工作表明，透彻了解结构与性能之间的关系对于合理设计和构建具有定制位点的合适催化剂以实现所需的催化反应至关重要。
{"title":"Intermetallic synergy in platinum–cobalt electrocatalysts for selective C–O bond cleavage","authors":"Ruizhi Wu, Qinglei Meng, Jiang Yan, Zhanrong Zhang, Bingfeng Chen, Huizhen Liu, Jing Tai, Guikai Zhang, Lirong Zheng, Jing Zhang, Buxing Han","doi":"10.1038/s41929-024-01165-w","DOIUrl":"10.1038/s41929-024-01165-w","url":null,"abstract":"Catalysts with tailored structures are crucial to determine the selectivity of chemical reactions. However, the design of catalyst structures for the selective cleavage of hydroxylic C–O(H) bonds while retaining etheric C–O(R) bonds remains a challenge and needs to be comprehensively explored. Here we report a series of mesoporous-carbon-supported platinum–cobalt (Pt–Co) bimetallic electrocatalysts in which different intermetallic interactions between Pt and Co species result in different hydrodeoxygenation and hydrogenation routes. Notably, Pt nanoparticles decorated with Co single atoms afford the selective cleavage of the C–O(H) bond in guaiacol and other lignin derivatives adjacent to an etheric C–O(R) bond with ether selectivities of >72.1%, and also work extensively for various other substrates with different substituents. This work highlights that a thorough understanding of the structure–performance relationship is crucial to rationally design and construct suitable catalysts with tailored sites for desired catalytic reactions. Being able to selectively derive desired compounds from biomass feedstock is very challenging. Now the selectivity of Pt–Co catalysts for the electroreduction of guaiacol and other lignin-derived substrates is shown to depend on the Co speciation and preferential C–OH cleavage can be obtained, retaining the C–OR group.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141159546","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}
Pub Date : 2024-05-24DOI: 10.1038/s41929-024-01162-z
Reginaldo J. Gomes, Ritesh Kumar, Hannah Fejzić, Bidushi Sarkar, Ishaan Roy, Chibueze V. Amanchukwu
Electrochemical carbon dioxide reduction (CO2R) can provide a sustainable route to produce fuels and chemicals; however, CO2R selectivity is frequently impaired by the competing hydrogen evolution reaction (HER), even for small concentrations of water. Here we tune water solvation and dynamics within a series of aprotic solvents featuring different functional groups and physicochemical properties to modulate HER activity and CO2R selectivity. We show that one can extend the HER onset potential by almost 1 V by confining water within a strong hydrogen bond network. We then achieve nearly 100% CO Faradaic efficiency at water concentrations as high as 3 M with a gold catalyst. Furthermore, under mildly acidic conditions, we sustain nearly 100% Faradaic efficiency towards CO with no carbonate losses over long-term electrolysis with an earth-abundant zinc catalyst. Our work provides insights to control water’s reactivity and reveals descriptors to guide electrolyte design for important electrochemical transformations. Electroreduction of CO2 competes with the hydrogen evolution reaction; thus, controlling water’s activity to exclusively act as a proton donor is a desirable yet challenging goal. Now the behaviour of water in aprotic solvents is shown to depend on the solvent’s donor ability, which can modulate the hydrogen bond network and in turn promote the desired reactivity.
电化学二氧化碳还原（CO2R）可以为生产燃料和化学品提供一条可持续发展的途径；然而，二氧化碳还原的选择性经常会受到相互竞争的氢进化反应（HER）的影响，即使在水的浓度很小的情况下也是如此。在这里，我们调整了一系列具有不同官能团和理化性质的钝化溶剂中水的溶解度和动力学，以调节 HER 活性和 CO2R 选择性。我们的研究表明，通过将水限制在强氢键网络中，可以将 HER 的起始电位提高近 1 V。然后，我们利用金催化剂在水浓度高达 3 M 的条件下实现了近 100% 的 CO 法拉第效率。此外，在弱酸性条件下，我们使用富土锌催化剂在长期电解过程中保持了近 100% 的 CO 法拉第效率，且无碳酸盐损失。我们的工作为控制水的反应性提供了见解，并揭示了指导重要电化学转化的电解质设计的描述符。
{"title":"Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations","authors":"Reginaldo J. Gomes, Ritesh Kumar, Hannah Fejzić, Bidushi Sarkar, Ishaan Roy, Chibueze V. Amanchukwu","doi":"10.1038/s41929-024-01162-z","DOIUrl":"10.1038/s41929-024-01162-z","url":null,"abstract":"Electrochemical carbon dioxide reduction (CO2R) can provide a sustainable route to produce fuels and chemicals; however, CO2R selectivity is frequently impaired by the competing hydrogen evolution reaction (HER), even for small concentrations of water. Here we tune water solvation and dynamics within a series of aprotic solvents featuring different functional groups and physicochemical properties to modulate HER activity and CO2R selectivity. We show that one can extend the HER onset potential by almost 1 V by confining water within a strong hydrogen bond network. We then achieve nearly 100% CO Faradaic efficiency at water concentrations as high as 3 M with a gold catalyst. Furthermore, under mildly acidic conditions, we sustain nearly 100% Faradaic efficiency towards CO with no carbonate losses over long-term electrolysis with an earth-abundant zinc catalyst. Our work provides insights to control water’s reactivity and reveals descriptors to guide electrolyte design for important electrochemical transformations. Electroreduction of CO2 competes with the hydrogen evolution reaction; thus, controlling water’s activity to exclusively act as a proton donor is a desirable yet challenging goal. Now the behaviour of water in aprotic solvents is shown to depend on the solvent’s donor ability, which can modulate the hydrogen bond network and in turn promote the desired reactivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141091864","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}
Pub Date : 2024-05-22DOI: 10.1038/s41929-024-01156-x
Zhihong Huang, Tao Cheng, Aamir Hassan Shah, Guangyan Zhong, Chengzhang Wan, Peiqi Wang, Mengning Ding, Jin Huang, Zhong Wan, Sibo Wang, Jin Cai, Bosi Peng, Haotian Liu, Yu Huang, William A. Goddard III, Xiangfeng Duan
Platinum nanocatalysts facilitate the hydrogen evolution reaction (HER) for renewable chemical fuel generation. These nanostructures encompass diverse surface sites, including (111) and (100) facets and edge sites between them. Identifying the exact active sites is essential for optimal catalyst design, but remains challenging. Here, combining electrical transport spectroscopy (ETS) with reactive force field (ReaxFF) calculations, we profile hydrogen adsorption on platinum nanowires and reveal two distinct peaks: one at 0.20 VRHE for (111) and (100) facets and one at 0.038 VRHE for edge sites. Concurrent ETS and cyclic voltammetry show that edge site adsorption coincides with the onset of the HER, indicating the critical role of edge sites. ReaxFF molecular dynamics calculations confirm lower activation barriers for the HER at edge sites, with two to four orders of magnitude higher turnover frequencies. ETS in alkaline media reveals substantially suppressed hydrogen adsorption on edge sites, contributing to the more sluggish HER kinetics. These findings resolve the elusive role of different sites on platinum surfaces, offering critical insights for HER catalyst design. Pt is the most active catalyst for the hydrogen evolution reaction in acidic media, but the precise nature of its active sites remains elusive. Now electrical transport spectroscopy and molecular dynamics are combined to map the hydrogen adsorption sites on Pt nanowires and reveal the much higher activity of (111)/(100) edge sites.
铂纳米催化剂可促进氢进化反应（HER），从而产生可再生化学燃料。这些纳米结构包含不同的表面位点，包括（111）和（100）面以及它们之间的边缘位点。确定确切的活性位点对于优化催化剂设计至关重要，但仍具有挑战性。在这里，我们将电迁移光谱（ETS）与反应力场（ReaxFF）计算相结合，对铂纳米线上的氢吸附进行了剖析，并发现了两个不同的峰值：一个在 0.20 VRHE 处为（111）和（100）面，另一个在 0.038 VRHE 处为边缘位点。同时进行的 ETS 和循环伏安分析表明，边缘位点的吸附与 HER 的发生相吻合，这表明边缘位点起着关键作用。ReaxFF 分子动力学计算证实，边缘位点的 HER 激活障碍较低，翻转频率高出 2 到 4 个数量级。碱性介质中的 ETS 显示，边缘位点上的氢吸附受到了极大的抑制，从而导致 HER 动力学更加缓慢。这些发现解决了铂表面不同位点难以捉摸的作用问题，为 HER 催化剂的设计提供了重要的启示。
{"title":"Edge sites dominate the hydrogen evolution reaction on platinum nanocatalysts","authors":"Zhihong Huang, Tao Cheng, Aamir Hassan Shah, Guangyan Zhong, Chengzhang Wan, Peiqi Wang, Mengning Ding, Jin Huang, Zhong Wan, Sibo Wang, Jin Cai, Bosi Peng, Haotian Liu, Yu Huang, William A. Goddard III, Xiangfeng Duan","doi":"10.1038/s41929-024-01156-x","DOIUrl":"10.1038/s41929-024-01156-x","url":null,"abstract":"Platinum nanocatalysts facilitate the hydrogen evolution reaction (HER) for renewable chemical fuel generation. These nanostructures encompass diverse surface sites, including (111) and (100) facets and edge sites between them. Identifying the exact active sites is essential for optimal catalyst design, but remains challenging. Here, combining electrical transport spectroscopy (ETS) with reactive force field (ReaxFF) calculations, we profile hydrogen adsorption on platinum nanowires and reveal two distinct peaks: one at 0.20 VRHE for (111) and (100) facets and one at 0.038 VRHE for edge sites. Concurrent ETS and cyclic voltammetry show that edge site adsorption coincides with the onset of the HER, indicating the critical role of edge sites. ReaxFF molecular dynamics calculations confirm lower activation barriers for the HER at edge sites, with two to four orders of magnitude higher turnover frequencies. ETS in alkaline media reveals substantially suppressed hydrogen adsorption on edge sites, contributing to the more sluggish HER kinetics. These findings resolve the elusive role of different sites on platinum surfaces, offering critical insights for HER catalyst design. Pt is the most active catalyst for the hydrogen evolution reaction in acidic media, but the precise nature of its active sites remains elusive. Now electrical transport spectroscopy and molecular dynamics are combined to map the hydrogen adsorption sites on Pt nanowires and reveal the much higher activity of (111)/(100) edge sites.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141079255","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}
Pub Date : 2024-05-15DOI: 10.1038/s41929-024-01155-y
Xiaomeng Dou, Tao Yan, Lixiang Qian, Huaming Hou, Miguel Lopez-Haro, Carlo Marini, Giovanni Agostini, Debora M. Meira, Xiangjie Zhang, Liang Zhang, Zhi Cao, Lichen Liu
Achieving the regioselective hydroformylation of linear α-olefins to linear aldehydes using solid catalysts with regioselectivities comparable to the corresponding homogeneous process is a great challenge in the chemical industry. Despite the tremendous efforts devoted to this research topic, most of the reported heterogeneous metal catalysts still give considerably lower regioselectivities than well-established homogeneous metal catalysts. Here we show the design of efficient Rh-zeolite catalysts, in which subnanometre Rh clusters are selectively confined in the sinusoidal ten-membered-ring channels of MFI zeolite, for the hydroformylation of long-chain linear α-olefins (C6–C12) into linear aldehydes with very high linear-to-branched aldehyde ratios (up to 400). The exceptional catalytic performances result from the involvement of the MFI zeolite framework as a rigid solid ligand that accommodates subnanometre Rh clusters in the sinusoidal channels of the MFI zeolite. Olefin hydroformylation is traditionally performed with homogeneous catalysts. Here the authors introduce a heterogeneous system based on zeolite-confined Rh clusters that is characterized by high efficiency for the hydroformylation of C6–C12 terminal olefins into linear aldehydes with high selectivity.
{"title":"Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite","authors":"Xiaomeng Dou, Tao Yan, Lixiang Qian, Huaming Hou, Miguel Lopez-Haro, Carlo Marini, Giovanni Agostini, Debora M. Meira, Xiangjie Zhang, Liang Zhang, Zhi Cao, Lichen Liu","doi":"10.1038/s41929-024-01155-y","DOIUrl":"10.1038/s41929-024-01155-y","url":null,"abstract":"Achieving the regioselective hydroformylation of linear α-olefins to linear aldehydes using solid catalysts with regioselectivities comparable to the corresponding homogeneous process is a great challenge in the chemical industry. Despite the tremendous efforts devoted to this research topic, most of the reported heterogeneous metal catalysts still give considerably lower regioselectivities than well-established homogeneous metal catalysts. Here we show the design of efficient Rh-zeolite catalysts, in which subnanometre Rh clusters are selectively confined in the sinusoidal ten-membered-ring channels of MFI zeolite, for the hydroformylation of long-chain linear α-olefins (C6–C12) into linear aldehydes with very high linear-to-branched aldehyde ratios (up to 400). The exceptional catalytic performances result from the involvement of the MFI zeolite framework as a rigid solid ligand that accommodates subnanometre Rh clusters in the sinusoidal channels of the MFI zeolite. Olefin hydroformylation is traditionally performed with homogeneous catalysts. Here the authors introduce a heterogeneous system based on zeolite-confined Rh clusters that is characterized by high efficiency for the hydroformylation of C6–C12 terminal olefins into linear aldehydes with high selectivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140925100","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}
Pub Date : 2024-05-07DOI: 10.1038/s41929-024-01160-1
Shengyang Ni, Riya Halder, Dilgam Ahmadli, Edward J. Reijerse, Josep Cornella, Tobias Ritter
Nickel photoredox catalysis has resulted in a rich development of transition-metal-catalysed transformations for carbon–heteroatom bond formation. By harnessing light energy, the transition metal can attain oxidation states that are difficult to achieve through thermal chemistry in a catalytic manifold. For example, nickel photoredox reactions have been reported for both the synthesis of anilines and aryl ethers from aryl(pseudo)halides. However, oxidative addition to simple nickel systems is often sluggish in the absence of special, electron-rich ligands, leading to catalyst decomposition. Electron-rich aryl electrophiles therefore currently fall outside the scope of many transformations in the field. Here we provide a conceptual solution to this problem and demonstrate nickel-catalysed C–heteroatom bond-forming reactions of arylthianthrenium salts, including amination, oxygenation, sulfuration and halogenation. Because the redox properties of arylthianthrenium salts are primarily dictated by the thianthrenium, oxidative addition of highly electron-rich aryl donors can be unlocked using simple NiCl2 under light irradiation to form the desired C‒heteroatom bonds. Photoredox-catalysed coupling of electron-rich aryl electrophiles based on simple nickel salts usually suffers from a slow oxidative addition. Now, it is shown that thianthrenation leads to more favourable redox properties of the substrates, alleviating this problem in carbon–heteroatom bond-forming reactions.
{"title":"C–heteroatom coupling with electron-rich aryls enabled by nickel catalysis and light","authors":"Shengyang Ni, Riya Halder, Dilgam Ahmadli, Edward J. Reijerse, Josep Cornella, Tobias Ritter","doi":"10.1038/s41929-024-01160-1","DOIUrl":"10.1038/s41929-024-01160-1","url":null,"abstract":"Nickel photoredox catalysis has resulted in a rich development of transition-metal-catalysed transformations for carbon–heteroatom bond formation. By harnessing light energy, the transition metal can attain oxidation states that are difficult to achieve through thermal chemistry in a catalytic manifold. For example, nickel photoredox reactions have been reported for both the synthesis of anilines and aryl ethers from aryl(pseudo)halides. However, oxidative addition to simple nickel systems is often sluggish in the absence of special, electron-rich ligands, leading to catalyst decomposition. Electron-rich aryl electrophiles therefore currently fall outside the scope of many transformations in the field. Here we provide a conceptual solution to this problem and demonstrate nickel-catalysed C–heteroatom bond-forming reactions of arylthianthrenium salts, including amination, oxygenation, sulfuration and halogenation. Because the redox properties of arylthianthrenium salts are primarily dictated by the thianthrenium, oxidative addition of highly electron-rich aryl donors can be unlocked using simple NiCl2 under light irradiation to form the desired C‒heteroatom bonds. Photoredox-catalysed coupling of electron-rich aryl electrophiles based on simple nickel salts usually suffers from a slow oxidative addition. Now, it is shown that thianthrenation leads to more favourable redox properties of the substrates, alleviating this problem in carbon–heteroatom bond-forming reactions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01160-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140845391","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}
Pub Date : 2024-05-03DOI: 10.1038/s41929-024-01149-w
Runze Mao, Shilong Gao, Zi-Yang Qin, Torben Rogge, Sophia J. Wu, Zi-Qi Li, Anuvab Das, K. N. Houk, Frances H. Arnold
Intermolecular functionalization of tertiary C–H bonds to construct fully substituted stereogenic carbon centres represents a formidable challenge: without the assistance of directing groups, state-of-the-art catalysts struggle to introduce chirality to racemic tertiary sp3-carbon centres. Direct asymmetric functionalization of such centres is a worthy reactivity and selectivity goal for modern biocatalysis. Here we present an engineered nitrene transferase (P411-TEA-5274), derived from a bacterial cytochrome P450, that is capable of aminating tertiary C–H bonds to provide chiral α-tertiary primary amines with high efficiency (up to 2,300 total turnovers) and selectivity (up to >99% enantiomeric excess). The construction of fully substituted stereocentres with methyl and ethyl groups underscores the enzyme’s remarkable selectivity. A comprehensive substrate scope study demonstrates the biocatalyst’s compatibility with diverse functional groups and tertiary C–H bonds. Mechanistic studies explain how active-site residues distinguish between the enantiomers and enable the enzyme to perform this transformation with excellent enantioselectivity. Direct stereoselective amination of tertiary C–H bonds without the assistance of directing groups is a challenging task in synthetic organic chemistry. Now a nitrene transferase is engineered to aminate tertiary C–H bonds with high enantioselectivity, providing direct access to valuable chiral α-tertiary primary amines.
{"title":"Biocatalytic, enantioenriched primary amination of tertiary C–H bonds","authors":"Runze Mao, Shilong Gao, Zi-Yang Qin, Torben Rogge, Sophia J. Wu, Zi-Qi Li, Anuvab Das, K. N. Houk, Frances H. Arnold","doi":"10.1038/s41929-024-01149-w","DOIUrl":"10.1038/s41929-024-01149-w","url":null,"abstract":"Intermolecular functionalization of tertiary C–H bonds to construct fully substituted stereogenic carbon centres represents a formidable challenge: without the assistance of directing groups, state-of-the-art catalysts struggle to introduce chirality to racemic tertiary sp3-carbon centres. Direct asymmetric functionalization of such centres is a worthy reactivity and selectivity goal for modern biocatalysis. Here we present an engineered nitrene transferase (P411-TEA-5274), derived from a bacterial cytochrome P450, that is capable of aminating tertiary C–H bonds to provide chiral α-tertiary primary amines with high efficiency (up to 2,300 total turnovers) and selectivity (up to >99% enantiomeric excess). The construction of fully substituted stereocentres with methyl and ethyl groups underscores the enzyme’s remarkable selectivity. A comprehensive substrate scope study demonstrates the biocatalyst’s compatibility with diverse functional groups and tertiary C–H bonds. Mechanistic studies explain how active-site residues distinguish between the enantiomers and enable the enzyme to perform this transformation with excellent enantioselectivity. Direct stereoselective amination of tertiary C–H bonds without the assistance of directing groups is a challenging task in synthetic organic chemistry. Now a nitrene transferase is engineered to aminate tertiary C–H bonds with high enantioselectivity, providing direct access to valuable chiral α-tertiary primary amines.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":37.8,"publicationDate":"2024-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140821088","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}
Pub Date : 2024-05-02DOI: 10.1038/s41929-024-01170-z
Christopher Fröhlich, H. Adrian Bunzel, Karol Buda, Adrian J. Mulholland, Marc W. van der Kamp, Pål J. Johnsen, Hanna-Kirsti S. Leiros, Nobuhiko Tokuriki
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