Pub Date : 2025-12-22DOI: 10.1038/s41929-025-01459-7
Christina N. Wiswell, David K. Tanas, Mitchell P. Croatt
Direct conversion of carboxylic acids to nitriles is desirable but thermodynamically uphill. Here, a bioinspired process utilizes magnesium and palladium co-catalysts and urea as a nitrogen source.
{"title":"Practical conversion of carboxylic acids to nitriles","authors":"Christina N. Wiswell, David K. Tanas, Mitchell P. Croatt","doi":"10.1038/s41929-025-01459-7","DOIUrl":"10.1038/s41929-025-01459-7","url":null,"abstract":"Direct conversion of carboxylic acids to nitriles is desirable but thermodynamically uphill. Here, a bioinspired process utilizes magnesium and palladium co-catalysts and urea as a nitrogen source.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1262-1263"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808786","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 : 2025-12-22DOI: 10.1038/s41929-025-01469-5
Benjamin Martindale
{"title":"Shining light using the dark","authors":"Benjamin Martindale","doi":"10.1038/s41929-025-01469-5","DOIUrl":"10.1038/s41929-025-01469-5","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1253-1253"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808787","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 : 2025-12-18DOI: 10.1038/s41929-025-01454-y
Manpreet Kaur, Sourav Rej, Jan Navrátil, Eva Yazmin Santiago, Michal Otyepka, Stefano Livraghi, Lorenzo Mino, Štěpán Kment, Zhikang Xu, Haibo Zhu, Paolo Fornasiero, Alexander O. Govorov, Piotr Błoński, Alberto Naldoni
Upgrading biomass feedstock into higher-value chemicals is central to improve the sustainability of the chemical industry and to reduce its dependence on fossil raw materials. Heterogeneous photocatalysts are promising for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a biomass-derived molecular platform for biopolymers, but their FDCA selectivity is negligible without the aid of a base. Here we present a plasmonic photocatalyst integrating TiN nanocubes and bimetallic RuPt nanoparticles that in base-free conditions exhibits complete HMF conversion and selective FDCA formation due to an unconventional mechanism of molecular oxygen activation. This unique reactivity is enhanced by both photothermal heating and hot electrons, whose contribution is confirmed by kinetic isotopic effect experiments. Density functional theory calculations support a scenario in which the activated nanoparticle–oxygen complex facilitates the rate-determining step and enables an improved FDCA selectivity. Our results demonstrate the potential of plasmonic photocatalysts in the catalytic transformation of biomass. Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O2 and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.
{"title":"Near-infrared plasmonic activation of molecular oxygen for selective oxidation of biomass derivatives","authors":"Manpreet Kaur, Sourav Rej, Jan Navrátil, Eva Yazmin Santiago, Michal Otyepka, Stefano Livraghi, Lorenzo Mino, Štěpán Kment, Zhikang Xu, Haibo Zhu, Paolo Fornasiero, Alexander O. Govorov, Piotr Błoński, Alberto Naldoni","doi":"10.1038/s41929-025-01454-y","DOIUrl":"10.1038/s41929-025-01454-y","url":null,"abstract":"Upgrading biomass feedstock into higher-value chemicals is central to improve the sustainability of the chemical industry and to reduce its dependence on fossil raw materials. Heterogeneous photocatalysts are promising for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a biomass-derived molecular platform for biopolymers, but their FDCA selectivity is negligible without the aid of a base. Here we present a plasmonic photocatalyst integrating TiN nanocubes and bimetallic RuPt nanoparticles that in base-free conditions exhibits complete HMF conversion and selective FDCA formation due to an unconventional mechanism of molecular oxygen activation. This unique reactivity is enhanced by both photothermal heating and hot electrons, whose contribution is confirmed by kinetic isotopic effect experiments. Density functional theory calculations support a scenario in which the activated nanoparticle–oxygen complex facilitates the rate-determining step and enables an improved FDCA selectivity. Our results demonstrate the potential of plasmonic photocatalysts in the catalytic transformation of biomass. Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O2 and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1370-1381"},"PeriodicalIF":44.6,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01454-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771399","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 : 2025-12-17DOI: 10.1038/s41929-025-01453-z
Martin Rihtaršič, Byeongseok Kweon, Piotr T. Błyszczyk, Alessandro Ruffoni, Enrique M. Arpa, Daniele Leonori
Energy transfer (EnT) catalysis enables the selective population of triplet excited states without previous singlet excitation, thus eliminating the need for high-energy irradiation. Traditionally, EnT catalysis has been approached by developing specific photosensitizers with triplet energies (ET) that match those of the targeted substrates. Here we introduce an alternative approach to EnT using widely available nitroarenes as photocatalysts. Our findings reveal that their catalytic efficiency is governed by the localization of their excited state rather than ET. Specifically, 3π,π* nitroarenes, where the excitation is centred on the aromatic core rather than the nitro group, exhibit superior catalytic performance compared with their 3n,π* counterparts. We have demonstrated the utility of this concept for nitroarene photocatalysis in contra-thermodynamic E-to-Z alkene isomerization and [2 + 2] cycloadditions. Additionally, we use the energetic descriptor ΔETT as easy tool to distinguish the preferential population of 3n,π* versus 3π,π* triplet states and therefore accelerate the identification of novel photosensitizers. Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.
{"title":"Excited-state configuration controls the ability of nitroarenes to act as energy transfer catalysts","authors":"Martin Rihtaršič, Byeongseok Kweon, Piotr T. Błyszczyk, Alessandro Ruffoni, Enrique M. Arpa, Daniele Leonori","doi":"10.1038/s41929-025-01453-z","DOIUrl":"10.1038/s41929-025-01453-z","url":null,"abstract":"Energy transfer (EnT) catalysis enables the selective population of triplet excited states without previous singlet excitation, thus eliminating the need for high-energy irradiation. Traditionally, EnT catalysis has been approached by developing specific photosensitizers with triplet energies (ET) that match those of the targeted substrates. Here we introduce an alternative approach to EnT using widely available nitroarenes as photocatalysts. Our findings reveal that their catalytic efficiency is governed by the localization of their excited state rather than ET. Specifically, 3π,π* nitroarenes, where the excitation is centred on the aromatic core rather than the nitro group, exhibit superior catalytic performance compared with their 3n,π* counterparts. We have demonstrated the utility of this concept for nitroarene photocatalysis in contra-thermodynamic E-to-Z alkene isomerization and [2 + 2] cycloadditions. Additionally, we use the energetic descriptor ΔETT as easy tool to distinguish the preferential population of 3n,π* versus 3π,π* triplet states and therefore accelerate the identification of novel photosensitizers. Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1361-1369"},"PeriodicalIF":44.6,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01453-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145765589","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 : 2025-12-12DOI: 10.1038/s41929-025-01451-1
Rafaël E. Vos, Pengfei Sun, Daniel Schauermann, Hassan Javed, Selwyn R. Hanselman, Gang Fu, Marc T. M. Koper
Future practical applications of the electrochemical CO2 reduction reaction will probably involve the use of higher pressures and temperatures. However, most research on the copper-catalysed electrochemical CO2 reduction reaction—the most widely studied system due to its C–C coupling ability—is typically performed under ambient conditions, and hence the mechanistic conclusions drawn also pertain to those conditions. Using a custom high-pressure, high-temperature electrochemical cell, we show here that on copper electrodes, the C–C coupling mechanism changes from the typical CO dimerization mechanism at low temperatures to a Fischer–Tropsch-like chain growth mechanism at temperatures above 125 °C (also requiring higher pressure). These results show that temperature and pressure are crucial parameters to consider in applied and mechanistic studies of the electrochemical reduction of CO2 because they can open up alternative reaction pathways and alter known mechanisms. Electrocatalytic CO2 reduction is typically studied at laboratory scale under ambient conditions; however, temperature and pressure may have a profound impact on the mechanism of this reaction and on its relevance to industrial applications. This study uses a custom temperature- and pressure-adjustable cell to reveal a chain growth mechanism emerging on copper electrodes at elevated temperatures and pressures.
{"title":"CO2 electroreduction on Cu operates via an alternative chain growth mechanism to form C–C bonds at elevated temperature and pressure","authors":"Rafaël E. Vos, Pengfei Sun, Daniel Schauermann, Hassan Javed, Selwyn R. Hanselman, Gang Fu, Marc T. M. Koper","doi":"10.1038/s41929-025-01451-1","DOIUrl":"10.1038/s41929-025-01451-1","url":null,"abstract":"Future practical applications of the electrochemical CO2 reduction reaction will probably involve the use of higher pressures and temperatures. However, most research on the copper-catalysed electrochemical CO2 reduction reaction—the most widely studied system due to its C–C coupling ability—is typically performed under ambient conditions, and hence the mechanistic conclusions drawn also pertain to those conditions. Using a custom high-pressure, high-temperature electrochemical cell, we show here that on copper electrodes, the C–C coupling mechanism changes from the typical CO dimerization mechanism at low temperatures to a Fischer–Tropsch-like chain growth mechanism at temperatures above 125 °C (also requiring higher pressure). These results show that temperature and pressure are crucial parameters to consider in applied and mechanistic studies of the electrochemical reduction of CO2 because they can open up alternative reaction pathways and alter known mechanisms. Electrocatalytic CO2 reduction is typically studied at laboratory scale under ambient conditions; however, temperature and pressure may have a profound impact on the mechanism of this reaction and on its relevance to industrial applications. This study uses a custom temperature- and pressure-adjustable cell to reveal a chain growth mechanism emerging on copper electrodes at elevated temperatures and pressures.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1338-1347"},"PeriodicalIF":44.6,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01451-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145746846","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 : 2025-12-05DOI: 10.1038/s41929-025-01452-0
Jun-Xiong He, Qi-Tao Lu, Tao Zhang, Rui-Yang Gao, Yun-Shu Cui, Yu Lan, Quan Cai
The Diels–Alder reaction is one of the most important reactions in organic synthesis, particularly when considering its ability to construct sp3-carbon-enriched carbocycles. Although extensive efforts have been dedicated to developing catalytic asymmetric variations of the Diels–Alder reaction, the generality of this textbook reaction is severely hindered by restrictive electronic requirements and substitution patterns. Here we disclose formal inverse-electron-demand [4+2] cycloadditions by transition metal catalysis. In these reactions, a single transition metal catalyst deploys two distinct processes, including generation and stabilization of transient electron-deficient dienes from Morita–Baylis–Hillman carbonates and promotion of subsequent [4+2] cycloadditions with external dienophiles. A wide range of para-substituted cyclohexenes are obtained in high yields with excellent chemo-, regio- and stereoselectivities by using 1,3-dienes as dienophiles via the catalysis of a Ni(0)–chiral monophosphine complex. This strategy is also extended to the Pd(0) catalysis, by which 1,3-enynes are compatible as dienophiles to afford chiral 1,4-cyclohexadienes with high enantioselectivities. Catalytic asymmetric all-carbon-based inverse-electron-demand Diels–Alder reactions are challenging. Now, transition metal catalysts enable formal inverse-electron-demand [4+2] cycloaddition reactions of Morita–Baylis–Hillman carbonates with 1,3-unsaturated compounds to afford chiral cyclohexene derivatives.
{"title":"Transition metal-catalysed [4+2] cycloadditions of Morita–Baylis–Hillman carbonates with 1,3-dienes and 1,3-enynes","authors":"Jun-Xiong He, Qi-Tao Lu, Tao Zhang, Rui-Yang Gao, Yun-Shu Cui, Yu Lan, Quan Cai","doi":"10.1038/s41929-025-01452-0","DOIUrl":"10.1038/s41929-025-01452-0","url":null,"abstract":"The Diels–Alder reaction is one of the most important reactions in organic synthesis, particularly when considering its ability to construct sp3-carbon-enriched carbocycles. Although extensive efforts have been dedicated to developing catalytic asymmetric variations of the Diels–Alder reaction, the generality of this textbook reaction is severely hindered by restrictive electronic requirements and substitution patterns. Here we disclose formal inverse-electron-demand [4+2] cycloadditions by transition metal catalysis. In these reactions, a single transition metal catalyst deploys two distinct processes, including generation and stabilization of transient electron-deficient dienes from Morita–Baylis–Hillman carbonates and promotion of subsequent [4+2] cycloadditions with external dienophiles. A wide range of para-substituted cyclohexenes are obtained in high yields with excellent chemo-, regio- and stereoselectivities by using 1,3-dienes as dienophiles via the catalysis of a Ni(0)–chiral monophosphine complex. This strategy is also extended to the Pd(0) catalysis, by which 1,3-enynes are compatible as dienophiles to afford chiral 1,4-cyclohexadienes with high enantioselectivities. Catalytic asymmetric all-carbon-based inverse-electron-demand Diels–Alder reactions are challenging. Now, transition metal catalysts enable formal inverse-electron-demand [4+2] cycloaddition reactions of Morita–Baylis–Hillman carbonates with 1,3-unsaturated compounds to afford chiral cyclohexene derivatives.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1348-1360"},"PeriodicalIF":44.6,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680743","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 : 2025-12-01DOI: 10.1038/s41929-025-01450-2
Yang Shi, Xiao Hai, Lei Cheng, Haolin Du, Xiaoye Yu, Hwee Ting Ang, Jiale Wu, Jinxing Chen, Gan Wang, Jiong Lu, Jie Wu
Cross-dehydrogenative coupling (CDC) reactions provide a facile approach for direct (hetero)aromatic C(sp2)−C and C(sp2)−heteroatom bond formation but conventionally rely on stoichiometric oxidants. Here we introduce single-platinum-atom-decorated graphitic carbon nitride (Pt-g-C3N4) as a recyclable heterogeneous photocatalyst for hydrogen-evolution CDC reactions between various (hetero)arenes and nucleophiles. Pt-g-C3N4 exhibits exceptional stability (10 cycles) with minimal platinum leaching (<0.02 ppm). Notably, the photocatalytic system showcases substantial utility and practicality in synthetic chemistry, enabling late-stage functionalization of pharmaceuticals and optoelectronic materials, and scalable (decagram) drug synthesis via a simple, in-house-built high-speed circulation flow system. Mechanistic investigations through control experiments and structural characterization elucidate the pivotal role of isolated platinum sites and substrate electronic properties in governing reaction selectivity. The integration of hydrogen-evolution CDC reactions with recyclable heterogeneous photocatalysis represents one of the greenest strategies for chemical synthesis, underscoring the promising future of single-atom catalysts as photocatalysts. Cross-dehydrogenative coupling (CDC) allows the efficient construction of C−C and C−heteroatom bonds. Now, single-platinum-atom-decorated graphitic carbon nitride is applied as a heterogeneous photocatalyst for CDC reactions between (hetero)arenes and nucleophiles without external oxidants.
{"title":"Single-atom photocatalysis boosting oxidant-free cross-dehydrogenative couplings of (hetero)arenes with nucleophiles","authors":"Yang Shi, Xiao Hai, Lei Cheng, Haolin Du, Xiaoye Yu, Hwee Ting Ang, Jiale Wu, Jinxing Chen, Gan Wang, Jiong Lu, Jie Wu","doi":"10.1038/s41929-025-01450-2","DOIUrl":"10.1038/s41929-025-01450-2","url":null,"abstract":"Cross-dehydrogenative coupling (CDC) reactions provide a facile approach for direct (hetero)aromatic C(sp2)−C and C(sp2)−heteroatom bond formation but conventionally rely on stoichiometric oxidants. Here we introduce single-platinum-atom-decorated graphitic carbon nitride (Pt-g-C3N4) as a recyclable heterogeneous photocatalyst for hydrogen-evolution CDC reactions between various (hetero)arenes and nucleophiles. Pt-g-C3N4 exhibits exceptional stability (10 cycles) with minimal platinum leaching (<0.02 ppm). Notably, the photocatalytic system showcases substantial utility and practicality in synthetic chemistry, enabling late-stage functionalization of pharmaceuticals and optoelectronic materials, and scalable (decagram) drug synthesis via a simple, in-house-built high-speed circulation flow system. Mechanistic investigations through control experiments and structural characterization elucidate the pivotal role of isolated platinum sites and substrate electronic properties in governing reaction selectivity. The integration of hydrogen-evolution CDC reactions with recyclable heterogeneous photocatalysis represents one of the greenest strategies for chemical synthesis, underscoring the promising future of single-atom catalysts as photocatalysts. Cross-dehydrogenative coupling (CDC) allows the efficient construction of C−C and C−heteroatom bonds. Now, single-platinum-atom-decorated graphitic carbon nitride is applied as a heterogeneous photocatalyst for CDC reactions between (hetero)arenes and nucleophiles without external oxidants.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1325-1337"},"PeriodicalIF":44.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645238","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 : 2025-11-25DOI: 10.1038/s41929-025-01447-x
Sergio Barranco, Inbal L. Eshel, Jiayu Zhang, Marco Di Matteo, Anat Milo, Mónica H. Pérez-Temprano
Directed hydrogen isotope exchange strategies have become an essential tool for accessing isotopically labelled organic scaffolds and interrogating the mechanisms of transition metal-catalysed C–H activation. However, the rationale behind deuterium source selection remains largely absent from the literature; an oversight that directly affects mechanistic interrogation strategies and hinders the development of new deuteration methodologies. Here we explore the influence of the deuterium source in base-assisted site-selective C–H deuteration reactions across a broad range of substrates using cobalt catalysis. We employ a synergistic combination of experimental studies and multivariable linear regression models based on proposed catalytic intermediates. Our findings demonstrate that the deuterium source can directly alter the operative mechanism, leading to distinct reaction pathways under different conditions. These results highlight previously overlooked complexity in hydrogen isotope exchange reactions and provide an example of how data-driven mechanistic analysis can expose subtle, reagent-dependent mechanistic shifts in catalytic behaviour. Directed hydrogen exchange is one of the main strategies for accessing isotopically labelled organic scaffolds, but the rationale for deuterium source selection has not been fully explored yet. Now the authors reveal the influence of the deuterium source in base-assisted site-selective C–H deuteration reactions across substrates in cobalt catalysis.
{"title":"Charting the influence of deuterium sources in hydrogen isotope exchange using a cobalt(III) catalytic platform","authors":"Sergio Barranco, Inbal L. Eshel, Jiayu Zhang, Marco Di Matteo, Anat Milo, Mónica H. Pérez-Temprano","doi":"10.1038/s41929-025-01447-x","DOIUrl":"10.1038/s41929-025-01447-x","url":null,"abstract":"Directed hydrogen isotope exchange strategies have become an essential tool for accessing isotopically labelled organic scaffolds and interrogating the mechanisms of transition metal-catalysed C–H activation. However, the rationale behind deuterium source selection remains largely absent from the literature; an oversight that directly affects mechanistic interrogation strategies and hinders the development of new deuteration methodologies. Here we explore the influence of the deuterium source in base-assisted site-selective C–H deuteration reactions across a broad range of substrates using cobalt catalysis. We employ a synergistic combination of experimental studies and multivariable linear regression models based on proposed catalytic intermediates. Our findings demonstrate that the deuterium source can directly alter the operative mechanism, leading to distinct reaction pathways under different conditions. These results highlight previously overlooked complexity in hydrogen isotope exchange reactions and provide an example of how data-driven mechanistic analysis can expose subtle, reagent-dependent mechanistic shifts in catalytic behaviour. Directed hydrogen exchange is one of the main strategies for accessing isotopically labelled organic scaffolds, but the rationale for deuterium source selection has not been fully explored yet. Now the authors reveal the influence of the deuterium source in base-assisted site-selective C–H deuteration reactions across substrates in cobalt catalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1306-1313"},"PeriodicalIF":44.6,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01447-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593781","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 : 2025-11-21DOI: 10.1038/s41929-025-01444-0
Naohiko Yoshikai
Bioactive piperidines are among the most common motifs in pharmaceuticals, yet accessing their chiral, highly substituted forms remains challenging. Now, a copper-catalysed reaction of amino-acid-derived cyclopropanols with aldehydes unites catalyst design with the natural chirality of reagents to access a broad family of stereodefined cis-2,6-disubstituted piperidines, expanding opportunities in drug discovery and natural product synthesis.
{"title":"Rewiring amino acids to piperidines","authors":"Naohiko Yoshikai","doi":"10.1038/s41929-025-01444-0","DOIUrl":"10.1038/s41929-025-01444-0","url":null,"abstract":"Bioactive piperidines are among the most common motifs in pharmaceuticals, yet accessing their chiral, highly substituted forms remains challenging. Now, a copper-catalysed reaction of amino-acid-derived cyclopropanols with aldehydes unites catalyst design with the natural chirality of reagents to access a broad family of stereodefined cis-2,6-disubstituted piperidines, expanding opportunities in drug discovery and natural product synthesis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1133-1134"},"PeriodicalIF":44.6,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561889","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 : 2025-11-21DOI: 10.1038/s41929-025-01443-1
Wenzhen Fu, Yang Yang
Engineering protein catalysts represents an attractive approach for enantioselective energy-transfer photochemistry. By combining a genetically encoded photosensitizer in the protein catalyst and a judiciously selected triplet quencher to suppress the racemic background reaction in the solution, photobiocatalytic [2+2] cycloaddition offers improved enantiocontrol in a triplet sensitization catalysis.
{"title":"Triplet quenchers for energy-transfer photobiocatalysis","authors":"Wenzhen Fu, Yang Yang","doi":"10.1038/s41929-025-01443-1","DOIUrl":"10.1038/s41929-025-01443-1","url":null,"abstract":"Engineering protein catalysts represents an attractive approach for enantioselective energy-transfer photochemistry. By combining a genetically encoded photosensitizer in the protein catalyst and a judiciously selected triplet quencher to suppress the racemic background reaction in the solution, photobiocatalytic [2+2] cycloaddition offers improved enantiocontrol in a triplet sensitization catalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1131-1132"},"PeriodicalIF":44.6,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561887","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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