Pub Date : 2024-09-24DOI: 10.1038/s41929-024-01224-2
Stefan Ringe
Methanol selectivity is uncommon among CO2 reduction electrocatalysts. A notable exception is the cobalt phthalocyanine catalyst supported on carbon nanotubes, yet the mechanism is still poorly understood. Now, two studies use a variety of analytical approaches to investigate the mechanism of the process including the role of alkali cations.
{"title":"Deciphering electrochemical methanol production","authors":"Stefan Ringe","doi":"10.1038/s41929-024-01224-2","DOIUrl":"10.1038/s41929-024-01224-2","url":null,"abstract":"Methanol selectivity is uncommon among CO2 reduction electrocatalysts. A notable exception is the cobalt phthalocyanine catalyst supported on carbon nanotubes, yet the mechanism is still poorly understood. Now, two studies use a variety of analytical approaches to investigate the mechanism of the process including the role of alkali cations.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"955-956"},"PeriodicalIF":42.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313976","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 : 2024-09-24DOI: 10.1038/s41929-024-01215-3
Jingchang Zhang, Magnus Rueping
Metallaphotoredox catalysis merging photocatalysis and transition metal catalysis is now the most efficient platform for sp3 C–H functionalizations due to its very efficient activation and transformation capability. In such a process, photocatalysis is usually in charge of C–H bond activation to generate an sp3-hybridized carbon-centred radical, whereas transition metal catalysis is in charge of the subsequent transformation of this radical. Here we review advances in sp3 C–H functionalizations under matallaphotoredox catalysis via photocatalytic single-electron transfer mechanisms as opposed to hydrogen atom transfer processes. The delineation of these advancements is initially organized according to distinct sp3 C–H bonds and subsequently categorized by various transition metal catalytic systems. We encompass a thorough exploration of diverse metallaphotoredox catalysis strategies, along with their synthetic applications and mechanisms. Similarities and differences between these strategies are described to inspire new reaction designs, thus promoting further development of this field. The merger of photocatalysis and transition metal catalysis has broadened the scope of chemical reactivity in organic synthesis. This Review provides an overview of the use of metallaphotoredox catalysis for sp3 C–H functionalizations that occur via single-electron, rather than hydrogen atom transfer.
{"title":"Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer","authors":"Jingchang Zhang, Magnus Rueping","doi":"10.1038/s41929-024-01215-3","DOIUrl":"10.1038/s41929-024-01215-3","url":null,"abstract":"Metallaphotoredox catalysis merging photocatalysis and transition metal catalysis is now the most efficient platform for sp3 C–H functionalizations due to its very efficient activation and transformation capability. In such a process, photocatalysis is usually in charge of C–H bond activation to generate an sp3-hybridized carbon-centred radical, whereas transition metal catalysis is in charge of the subsequent transformation of this radical. Here we review advances in sp3 C–H functionalizations under matallaphotoredox catalysis via photocatalytic single-electron transfer mechanisms as opposed to hydrogen atom transfer processes. The delineation of these advancements is initially organized according to distinct sp3 C–H bonds and subsequently categorized by various transition metal catalytic systems. We encompass a thorough exploration of diverse metallaphotoredox catalysis strategies, along with their synthetic applications and mechanisms. Similarities and differences between these strategies are described to inspire new reaction designs, thus promoting further development of this field. The merger of photocatalysis and transition metal catalysis has broadened the scope of chemical reactivity in organic synthesis. This Review provides an overview of the use of metallaphotoredox catalysis for sp3 C–H functionalizations that occur via single-electron, rather than hydrogen atom transfer.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"963-976"},"PeriodicalIF":42.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313979","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 : 2024-09-24DOI: 10.1038/s41929-024-01223-3
Yuting Wang, Bin Zhang
Electrochemical nitrate reduction to ammonia is a promising approach for waste conversion, yet the use of a concentrated supporting electrolyte creates a product separation issue. Now, a porous solid electrolyte reactor with a cation shielding effect is reported for nitrate wastewater treatment and the production of pure ammonia.
{"title":"Solid electrolyte reactor for nitrate-to-ammonia","authors":"Yuting Wang, Bin Zhang","doi":"10.1038/s41929-024-01223-3","DOIUrl":"10.1038/s41929-024-01223-3","url":null,"abstract":"Electrochemical nitrate reduction to ammonia is a promising approach for waste conversion, yet the use of a concentrated supporting electrolyte creates a product separation issue. Now, a porous solid electrolyte reactor with a cation shielding effect is reported for nitrate wastewater treatment and the production of pure ammonia.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"959-960"},"PeriodicalIF":42.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313791","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 : 2024-09-24DOI: 10.1038/s41929-024-01217-1
Nikolay Kornienko
Electrifying the fragmentation of hydrocarbons is an emerging challenge in the context of decarbonizing the chemical industry. To this end, competing electrocatalytic C–C cleavage and oxidation pathways of butane were investigated.
{"title":"Unlocking C–C cleavage in the electrochemical toolbox","authors":"Nikolay Kornienko","doi":"10.1038/s41929-024-01217-1","DOIUrl":"10.1038/s41929-024-01217-1","url":null,"abstract":"Electrifying the fragmentation of hydrocarbons is an emerging challenge in the context of decarbonizing the chemical industry. To this end, competing electrocatalytic C–C cleavage and oxidation pathways of butane were investigated.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"957-958"},"PeriodicalIF":42.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313794","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 : 2024-09-24DOI: 10.1038/s41929-024-01216-2
Jinhyeong Jang, Elena A. Rozhkova
A photodiode can trigger bias-free redox reactions but is often hindered by thermodynamic barriers. Now, a bacteria-conjugated silicon biophotochemical diode allows simultaneous conversion of various carbon molecules with high efficacy.
{"title":"Carbon conversion on biophotonic leaf","authors":"Jinhyeong Jang, Elena A. Rozhkova","doi":"10.1038/s41929-024-01216-2","DOIUrl":"10.1038/s41929-024-01216-2","url":null,"abstract":"A photodiode can trigger bias-free redox reactions but is often hindered by thermodynamic barriers. Now, a bacteria-conjugated silicon biophotochemical diode allows simultaneous conversion of various carbon molecules with high efficacy.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"953-954"},"PeriodicalIF":42.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313978","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 : 2024-09-23DOI: 10.1038/s41929-024-01227-z
Yifei Xu, Zhaoming Xia, Wenqiang Gao, Hai Xiao, Bingjun Xu
The nature of the cations in an electrolyte has a substantial impact on the performance of the electrochemical CO2 and CO reduction reaction (CO(2)RR), however, its mechanism at the molecular level remains the subject of debate. Major gaps in our understanding include how cations affect key physicochemical variables at electrochemical interfaces and the elementary steps of the CO(2)RR. In this work, we have quantitatively determined the impact of cations on the enthalpy and entropy of CO adsorption on Cu under electrochemical conditions. CO adsorption becomes increasingly unfavourable in the sequence Li+ > Na+ > K+ > Cs+ with a substantial enthalpy–entropy compensation effect. Importantly, cations affect the stability of the initial and transition states of the CORR in opposite directions. Our results provide insights into the effect of cations on individual elementary steps in the CORR and demonstrate that the ability to stabilize the transition state in the conversion of adsorbed CO is a decisive factor. The mechanism of electrocatalytic CO/CO2 reduction on Cu surfaces is complex and its various mechanisms remain under debate, including the important role of cations in the electrolyte. Here the authors quantitatively determine the impact of alkali cations on the thermodynamics of CO adsorption under electrochemical conditions and the activation parameters of the rate-determining step.
电解质中阳离子的性质对二氧化碳和一氧化碳电化学还原反应（CO(2)RR）的性能有重大影响，但其分子水平上的机理仍存在争议。我们对阳离子如何影响电化学界面上的关键物理化学变量以及 CO(2)RR 的基本步骤的理解还存在很大差距。在这项工作中，我们定量测定了阳离子对电化学条件下 CO 在铜上吸附的焓和熵的影响。在 Li+ > Na+ > K+ > Cs+ 的序列中，CO 的吸附变得越来越不利，并产生了很大的焓熵补偿效应。重要的是，阳离子以相反的方向影响 CORR 初始状态和过渡状态的稳定性。我们的研究结果让我们深入了解了阳离子对 CORR 中各个基本步骤的影响，并证明了在吸附 CO 的转化过程中稳定过渡态的能力是一个决定性因素。
{"title":"Cation effect on the elementary steps of the electrochemical CO reduction reaction on Cu","authors":"Yifei Xu, Zhaoming Xia, Wenqiang Gao, Hai Xiao, Bingjun Xu","doi":"10.1038/s41929-024-01227-z","DOIUrl":"10.1038/s41929-024-01227-z","url":null,"abstract":"The nature of the cations in an electrolyte has a substantial impact on the performance of the electrochemical CO2 and CO reduction reaction (CO(2)RR), however, its mechanism at the molecular level remains the subject of debate. Major gaps in our understanding include how cations affect key physicochemical variables at electrochemical interfaces and the elementary steps of the CO(2)RR. In this work, we have quantitatively determined the impact of cations on the enthalpy and entropy of CO adsorption on Cu under electrochemical conditions. CO adsorption becomes increasingly unfavourable in the sequence Li+ > Na+ > K+ > Cs+ with a substantial enthalpy–entropy compensation effect. Importantly, cations affect the stability of the initial and transition states of the CORR in opposite directions. Our results provide insights into the effect of cations on individual elementary steps in the CORR and demonstrate that the ability to stabilize the transition state in the conversion of adsorbed CO is a decisive factor. The mechanism of electrocatalytic CO/CO2 reduction on Cu surfaces is complex and its various mechanisms remain under debate, including the important role of cations in the electrolyte. Here the authors quantitatively determine the impact of alkali cations on the thermodynamics of CO adsorption under electrochemical conditions and the activation parameters of the rate-determining step.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1120-1129"},"PeriodicalIF":42.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276783","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 : 2024-09-19DOI: 10.1038/s41929-024-01229-x
Joseph B. Solomon, Chi Chung Lee, Yiling A. Liu, Calder Duffin, Markus W. Ribbe, Yilin Hu
Heterologous expression of nitrogenase has been actively pursued because of the far-reaching impact of this enzyme on agriculture, energy and the environment. However, isolation of an active two-component, metallocentre-containing nitrogenase from a non-diazotrophic host has yet to be accomplished. Here we report the heterologous synthesis of an active molybdenum-nitrogenase by combining genes from Azotobacter vinelandii and Methanosarcina acetivorans in Escherichia coli. Metal, activity and electron paramagnetic resonance analyses demonstrate the integrity of the metallocentres in the purified nitrogenase enzyme; whereas growth, nanoscale secondary ion mass spectrometry and nuclear magnetic resonance experiments illustrate diazotrophic growth and 15N enrichment by the E. coli expression strain, and accumulation of extracellular ammonia upon deletion of the ammonia transporter that permits incorporation of thus-generated nitrogen into the cellular mass of a non-diazotrophic E. coli strain. As such, this study provides a crucial prototype system that could be optimized/modified to enable future transgenic expression and biotechnological adaptations of nitrogenase. Heterologous expression of an active, metallocentre-containing nitrogenase in a non-diazotrophic host is challenging. Now, the heterologous biosynthetic pathway of Mo-nitrogenase is pieced together in Escherichia coli using genes from Azotobacter vinelandii and Methanosarcina acetivorans.
{"title":"Ammonia synthesis via an engineered nitrogenase assembly pathway in Escherichia coli","authors":"Joseph B. Solomon, Chi Chung Lee, Yiling A. Liu, Calder Duffin, Markus W. Ribbe, Yilin Hu","doi":"10.1038/s41929-024-01229-x","DOIUrl":"10.1038/s41929-024-01229-x","url":null,"abstract":"Heterologous expression of nitrogenase has been actively pursued because of the far-reaching impact of this enzyme on agriculture, energy and the environment. However, isolation of an active two-component, metallocentre-containing nitrogenase from a non-diazotrophic host has yet to be accomplished. Here we report the heterologous synthesis of an active molybdenum-nitrogenase by combining genes from Azotobacter vinelandii and Methanosarcina acetivorans in Escherichia coli. Metal, activity and electron paramagnetic resonance analyses demonstrate the integrity of the metallocentres in the purified nitrogenase enzyme; whereas growth, nanoscale secondary ion mass spectrometry and nuclear magnetic resonance experiments illustrate diazotrophic growth and 15N enrichment by the E. coli expression strain, and accumulation of extracellular ammonia upon deletion of the ammonia transporter that permits incorporation of thus-generated nitrogen into the cellular mass of a non-diazotrophic E. coli strain. As such, this study provides a crucial prototype system that could be optimized/modified to enable future transgenic expression and biotechnological adaptations of nitrogenase. Heterologous expression of an active, metallocentre-containing nitrogenase in a non-diazotrophic host is challenging. Now, the heterologous biosynthetic pathway of Mo-nitrogenase is pieced together in Escherichia coli using genes from Azotobacter vinelandii and Methanosarcina acetivorans.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1130-1141"},"PeriodicalIF":42.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142245766","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 : 2024-09-19DOI: 10.1038/s41929-024-01219-z
Karma Zuraiqi, Yichao Jin, Caiden J. Parker, Jaydon Meilak, Nastaran Meftahi, Andrew J. Christofferson, Salvy P. Russo, Michelle J. S. Spencer, Huai Yong Zhu, Lizhuo Wang, Jun Huang, Rosalie K. Hocking, Ken Chiang, Sarina Sarina, Torben Daeneke
The outlook for sustainable economic and ecological growth projects an ammonia economy as a key enabler to the energy transition landscape. The predominance of the Haber–Bosch process, however, as the current industrial process for producing ammonia subdues the sustainability of establishing an energy route predicated on ammonia. Here we capitalize on the inherent atomic structure of liquid metal alloys and the ability to modulate the electronic and geometric structures of liquid metal catalysts to drive the thermocatalytic synthesis of ammonia. By exploiting the mobility of the metal atoms in the liquid metal configuration and purposefully designing disordered metal catalysts, we provide insights into designing future transition metal-based catalysts that produce ammonia from gaseous nitrogen and hydrogen under mild operating conditions. The use of a molten Cu–Ga catalyst offers a dynamic metal complex with synergistic advantages that lift the activity of its constituent elements, exceeding the activity of a control Ru-based catalyst. The traditional Haber–Bosch process as well as recent alternative approaches based on photo- or electrocatalysis all rely on solid catalysts to convert nitrogen into ammonia. Here the authors disclose an effective method for the synthesis of this crucial commodity based on a Cu–Ga liquid metal catalyst instead.
{"title":"Unveiling metal mobility in a liquid Cu–Ga catalyst for ammonia synthesis","authors":"Karma Zuraiqi, Yichao Jin, Caiden J. Parker, Jaydon Meilak, Nastaran Meftahi, Andrew J. Christofferson, Salvy P. Russo, Michelle J. S. Spencer, Huai Yong Zhu, Lizhuo Wang, Jun Huang, Rosalie K. Hocking, Ken Chiang, Sarina Sarina, Torben Daeneke","doi":"10.1038/s41929-024-01219-z","DOIUrl":"10.1038/s41929-024-01219-z","url":null,"abstract":"The outlook for sustainable economic and ecological growth projects an ammonia economy as a key enabler to the energy transition landscape. The predominance of the Haber–Bosch process, however, as the current industrial process for producing ammonia subdues the sustainability of establishing an energy route predicated on ammonia. Here we capitalize on the inherent atomic structure of liquid metal alloys and the ability to modulate the electronic and geometric structures of liquid metal catalysts to drive the thermocatalytic synthesis of ammonia. By exploiting the mobility of the metal atoms in the liquid metal configuration and purposefully designing disordered metal catalysts, we provide insights into designing future transition metal-based catalysts that produce ammonia from gaseous nitrogen and hydrogen under mild operating conditions. The use of a molten Cu–Ga catalyst offers a dynamic metal complex with synergistic advantages that lift the activity of its constituent elements, exceeding the activity of a control Ru-based catalyst. The traditional Haber–Bosch process as well as recent alternative approaches based on photo- or electrocatalysis all rely on solid catalysts to convert nitrogen into ammonia. Here the authors disclose an effective method for the synthesis of this crucial commodity based on a Cu–Ga liquid metal catalyst instead.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"1044-1052"},"PeriodicalIF":42.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142245680","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 : 2024-09-13DOI: 10.1038/s41929-024-01225-1
Maryam Abdinejad, Amirhossein Farzi, Robin Möller-Gulland, Fokko Mulder, Chengyu Liu, Junming Shao, Jasper Biemolt, Marc Robert, Ali Seifitokaldani, Thomas Burdyny
Molecular catalysts play a significant role in chemical transformations, utilizing changes in redox states to facilitate reactions. To date molecular electrocatalysts have efficiently produced single-carbon products from CO2 but have struggled to achieve a carbon–carbon coupling step. Conversely, copper catalysts can enable carbon–carbon coupling, but lead to broad C2+ product spectra. Here we subvert the traditional redox-mediated reaction mechanisms of organometallic compounds through a heterogeneous nickel-supported iron tetraphenylporphyrin electrocatalyst, facilitating electrochemical carbon–carbon coupling to produce ethanol. This represents a marked behavioural shift compared with carbon-supported metalloporphyrins. Extending the approach to a three-dimensional porous nickel support with adsorbed iron tetraphenylporphyrin, we attain ethanol Faradaic efficiencies of 68% ± 3.2% at −0.3 V versus a reversible hydrogen electrode (pH 7.7) with partial ethanol current densities of −21 mA cm−2. Separately we demonstrate maintained ethanol production over 60 h of operation. Further consideration of the wide parameter space of molecular catalyst and metal electrodes shows promise for additional chemistries and achievable metrics. The electrochemical reduction of CO2 on organometallic catalysts is commonly limited to two-electron products. Now, an iron tetraphenylporphyrin catalyst immobilized onto a nickel electrode is shown to achieve a Faradaic efficiency for ethanol of 68% due to the strong electronic coupling between the catalyst and the support.
{"title":"Eliminating redox-mediated electron transfer mechanisms on a supported molecular catalyst enables CO2 conversion to ethanol","authors":"Maryam Abdinejad, Amirhossein Farzi, Robin Möller-Gulland, Fokko Mulder, Chengyu Liu, Junming Shao, Jasper Biemolt, Marc Robert, Ali Seifitokaldani, Thomas Burdyny","doi":"10.1038/s41929-024-01225-1","DOIUrl":"10.1038/s41929-024-01225-1","url":null,"abstract":"Molecular catalysts play a significant role in chemical transformations, utilizing changes in redox states to facilitate reactions. To date molecular electrocatalysts have efficiently produced single-carbon products from CO2 but have struggled to achieve a carbon–carbon coupling step. Conversely, copper catalysts can enable carbon–carbon coupling, but lead to broad C2+ product spectra. Here we subvert the traditional redox-mediated reaction mechanisms of organometallic compounds through a heterogeneous nickel-supported iron tetraphenylporphyrin electrocatalyst, facilitating electrochemical carbon–carbon coupling to produce ethanol. This represents a marked behavioural shift compared with carbon-supported metalloporphyrins. Extending the approach to a three-dimensional porous nickel support with adsorbed iron tetraphenylporphyrin, we attain ethanol Faradaic efficiencies of 68% ± 3.2% at −0.3 V versus a reversible hydrogen electrode (pH 7.7) with partial ethanol current densities of −21 mA cm−2. Separately we demonstrate maintained ethanol production over 60 h of operation. Further consideration of the wide parameter space of molecular catalyst and metal electrodes shows promise for additional chemistries and achievable metrics. The electrochemical reduction of CO2 on organometallic catalysts is commonly limited to two-electron products. Now, an iron tetraphenylporphyrin catalyst immobilized onto a nickel electrode is shown to achieve a Faradaic efficiency for ethanol of 68% due to the strong electronic coupling between the catalyst and the support.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1109-1119"},"PeriodicalIF":42.8,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142174943","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 : 2024-09-09DOI: 10.1038/s41929-024-01213-5
Qingjin Liang, Xinping Zhang, Madeline E. Rotella, Zeyu Xu, Marisa C. Kozlowski, Tiezheng Jia
Sulfur stereogenic molecules have a significant impact on drug development. Among them, sulfilimines are chiral molecules bearing S(IV) stereocentres, which exhibit great value in chemistry and biology but have so far been synthetically challenging to achieve. Similarly, it has also been a challenge to control the stereochemistry in Chan–Lam coupling, which has been widely used to construct C–N, C–O and C–S bonds by coupling nucleophiles with boronic acids using copper complexes. Here we report a highly chemoselective and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids to deliver an array of thermodynamically disfavoured aryl sulfilimines containing a sulfur stereocentre. A copper catalyst from a 2-pyridyl N-phenyl dihydroimidazole ligand has been designed that enables effective enantiocontrol by means of a well-defined chiral environment and high reactivity that outcompetes the background racemic transformation. A combined experimental and computational study establishes the reaction mechanism and unveils the origin of chemoselectivity and stereoselectivity. Sulfilimines are a class of chiral molecules that bear S(IV) stereocentres, which are of high value in drug discovery but difficult to synthesize. Now the authors report a chemo- and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids that delivers diaryl and alkyl aryl sulfilimines.
{"title":"Enantioselective Chan–Lam S-arylation of sulfenamides","authors":"Qingjin Liang, Xinping Zhang, Madeline E. Rotella, Zeyu Xu, Marisa C. Kozlowski, Tiezheng Jia","doi":"10.1038/s41929-024-01213-5","DOIUrl":"10.1038/s41929-024-01213-5","url":null,"abstract":"Sulfur stereogenic molecules have a significant impact on drug development. Among them, sulfilimines are chiral molecules bearing S(IV) stereocentres, which exhibit great value in chemistry and biology but have so far been synthetically challenging to achieve. Similarly, it has also been a challenge to control the stereochemistry in Chan–Lam coupling, which has been widely used to construct C–N, C–O and C–S bonds by coupling nucleophiles with boronic acids using copper complexes. Here we report a highly chemoselective and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids to deliver an array of thermodynamically disfavoured aryl sulfilimines containing a sulfur stereocentre. A copper catalyst from a 2-pyridyl N-phenyl dihydroimidazole ligand has been designed that enables effective enantiocontrol by means of a well-defined chiral environment and high reactivity that outcompetes the background racemic transformation. A combined experimental and computational study establishes the reaction mechanism and unveils the origin of chemoselectivity and stereoselectivity. Sulfilimines are a class of chiral molecules that bear S(IV) stereocentres, which are of high value in drug discovery but difficult to synthesize. Now the authors report a chemo- and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids that delivers diaryl and alkyl aryl sulfilimines.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"1010-1020"},"PeriodicalIF":42.8,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142158829","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}
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