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}
Pub Date : 2025-11-21DOI: 10.1038/s41929-025-01442-2
Shusen Chen, Huimei Huang, Ning Fang
The rational design of electrocatalysts for hydrogen-involving transformations requires a detailed understanding of surface metal-hydrogen intermediates at the single-site level. Now, single-molecule fluorescence microscopy enables the direct visualization of these intermediates and reveals inter- and intra-particle heterogeneity during the hydrogen evolution reaction on Pd nanocubes.
{"title":"A single-molecule view of surface Pd–H*","authors":"Shusen Chen, Huimei Huang, Ning Fang","doi":"10.1038/s41929-025-01442-2","DOIUrl":"10.1038/s41929-025-01442-2","url":null,"abstract":"The rational design of electrocatalysts for hydrogen-involving transformations requires a detailed understanding of surface metal-hydrogen intermediates at the single-site level. Now, single-molecule fluorescence microscopy enables the direct visualization of these intermediates and reveals inter- and intra-particle heterogeneity during the hydrogen evolution reaction on Pd nanocubes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1129-1130"},"PeriodicalIF":44.6,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145561888","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 : 2025-11-20DOI: 10.1038/s41929-025-01431-5
Kallol Mukherjee, Ayala Ben David, Hasmik Nikoghosyan, Robert Hakobyan, Vladimir Gevorgyan
Selective conversion of C–H bonds into high-value functional groups is a highly desirable process. Hydrogen atom transfer (HAT) is a powerful approach towards this goal by offering straightforward access to open-shell radical intermediates directly from R–H bonds. Recently, a subclass of photocatalysis referred to as visible-light-induced transition metal (TM) catalysis has emerged as a distinctive synthetic tool. This enables TMs to serve a dual role: capturing light energy and driving catalytic transformations. This dual functionality has been increasingly utilized to execute HAT without requiring an external photosensitizer. Although cooperative photocatalysis involving photoredox and TM catalysis contributed to early developments in this area, visible-light-induced TM catalysis offers direct and versatile approaches to C–H functionalization. In the past few years, this methodology has been extensively used to execute HAT. Here we describe the early development and recent advances of photoexcited-transition-metal-catalysed HAT processes. This Review covers the recent advances in the field of hydrogen atom transfer catalysis mediated by photoexcited transition metals without the use of external photosensitizers.
{"title":"Light-induced transition-metal-catalysed hydrogen atom transfer in organic transformations","authors":"Kallol Mukherjee, Ayala Ben David, Hasmik Nikoghosyan, Robert Hakobyan, Vladimir Gevorgyan","doi":"10.1038/s41929-025-01431-5","DOIUrl":"10.1038/s41929-025-01431-5","url":null,"abstract":"Selective conversion of C–H bonds into high-value functional groups is a highly desirable process. Hydrogen atom transfer (HAT) is a powerful approach towards this goal by offering straightforward access to open-shell radical intermediates directly from R–H bonds. Recently, a subclass of photocatalysis referred to as visible-light-induced transition metal (TM) catalysis has emerged as a distinctive synthetic tool. This enables TMs to serve a dual role: capturing light energy and driving catalytic transformations. This dual functionality has been increasingly utilized to execute HAT without requiring an external photosensitizer. Although cooperative photocatalysis involving photoredox and TM catalysis contributed to early developments in this area, visible-light-induced TM catalysis offers direct and versatile approaches to C–H functionalization. In the past few years, this methodology has been extensively used to execute HAT. Here we describe the early development and recent advances of photoexcited-transition-metal-catalysed HAT processes. This Review covers the recent advances in the field of hydrogen atom transfer catalysis mediated by photoexcited transition metals without the use of external photosensitizers.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1146-1158"},"PeriodicalIF":44.6,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560407","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 : 2025-11-18DOI: 10.1038/s41929-025-01446-y
Junhong Meng, Mithun C. Madhusudhanan, Teng Wang, Zengrui Cheng, Binzhi Zhao, Hongwei Shi, Licheng Yang, Peng Liu, Ning Jiao
The direct synthetic approach from versatile and abundantly sourced carboxylic acids to nitriles has garnered considerable attention for a long time. However, the highly unfavourable thermodynamics of this process make it challenging to achieve under mild conditions and with broad functional-group tolerance. Here, inspired by biosynthetic pathways of nitrile synthesis and urea activation, we present a mild Mg- and Pd-cocatalysed nitrile synthesis from carboxylic acids with the simple, inexpensive and readily available urea as the nitrogen source. A pathway involving nucleophilic addition of carboxylic acid to urea is supported by both mechanistic studies and density functional theory calculations. This chemistry also demonstrates efficiency for the late-stage modification of complex drugs and natural products and offers substantial opportunities for the synthesis and optimization of valuable compounds. There is growing interest in the direct conversion of carboxylic acids into nitriles. Now the authors report a mild Mg- and Pd-cocatalysed method compatible with multiple functional groups, using urea as the nitrogen source.
{"title":"Late-stage conversion of carboxylic acids to nitriles with Mg and Pd cocatalysis","authors":"Junhong Meng, Mithun C. Madhusudhanan, Teng Wang, Zengrui Cheng, Binzhi Zhao, Hongwei Shi, Licheng Yang, Peng Liu, Ning Jiao","doi":"10.1038/s41929-025-01446-y","DOIUrl":"10.1038/s41929-025-01446-y","url":null,"abstract":"The direct synthetic approach from versatile and abundantly sourced carboxylic acids to nitriles has garnered considerable attention for a long time. However, the highly unfavourable thermodynamics of this process make it challenging to achieve under mild conditions and with broad functional-group tolerance. Here, inspired by biosynthetic pathways of nitrile synthesis and urea activation, we present a mild Mg- and Pd-cocatalysed nitrile synthesis from carboxylic acids with the simple, inexpensive and readily available urea as the nitrogen source. A pathway involving nucleophilic addition of carboxylic acid to urea is supported by both mechanistic studies and density functional theory calculations. This chemistry also demonstrates efficiency for the late-stage modification of complex drugs and natural products and offers substantial opportunities for the synthesis and optimization of valuable compounds. There is growing interest in the direct conversion of carboxylic acids into nitriles. Now the authors report a mild Mg- and Pd-cocatalysed method compatible with multiple functional groups, using urea as the nitrogen source.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1295-1305"},"PeriodicalIF":44.6,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536706","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 : 2025-11-18DOI: 10.1038/s41929-025-01445-z
Linfeng An, Shanshan Li, Kaiming Zhang
RNA’s regulatory and catalytic roles affect gene expression, with circular RNAs (circRNAs) emerging as a unique subclass with broad therapeutic potential. Among circRNA production methods, ribozyme-mediated circularization, especially through group I intron-based systems such as the T4 td-PIE (where PIE indicates permuted intron–exon), offers efficient in vitro synthesis. However, detailed structural insights of the T4 td intron are limited, particularly regarding circularization mechanisms. Here we use cryo-electron microscopy to resolve high-resolution structures of both linear and circular T4 td intron forms. Comparative structural analysis reveals key conformational shifts in the catalytic core, including P1ext domain loss and realignment of critical base pairs in the circular form. Additionally, we identify critical sites and interactions optimizing RNA circularization. Structure-guided mutations enhance circularization efficiency, as validated in the T4 td-PIE system and benchmarked against alternative platforms. These findings enhance our understanding of RNA circularization mechanisms and inform optimizations for large-scale circRNA production, with important implications for RNA-based therapeutics and synthetic biology. The T4 td-PIE system is a promising platform for circular RNA synthesis, but the dynamic mechanism of the T4 td group I intron during circularization remains unclear. Now, cryo-EM structures of both the linear and circular forms of the T4 td intron are solved, revealing key conformational shifts essential for RNA circularization.
{"title":"Structural insights and engineering of the T4 td intron for improved RNA circularization","authors":"Linfeng An, Shanshan Li, Kaiming Zhang","doi":"10.1038/s41929-025-01445-z","DOIUrl":"10.1038/s41929-025-01445-z","url":null,"abstract":"RNA’s regulatory and catalytic roles affect gene expression, with circular RNAs (circRNAs) emerging as a unique subclass with broad therapeutic potential. Among circRNA production methods, ribozyme-mediated circularization, especially through group I intron-based systems such as the T4 td-PIE (where PIE indicates permuted intron–exon), offers efficient in vitro synthesis. However, detailed structural insights of the T4 td intron are limited, particularly regarding circularization mechanisms. Here we use cryo-electron microscopy to resolve high-resolution structures of both linear and circular T4 td intron forms. Comparative structural analysis reveals key conformational shifts in the catalytic core, including P1ext domain loss and realignment of critical base pairs in the circular form. Additionally, we identify critical sites and interactions optimizing RNA circularization. Structure-guided mutations enhance circularization efficiency, as validated in the T4 td-PIE system and benchmarked against alternative platforms. These findings enhance our understanding of RNA circularization mechanisms and inform optimizations for large-scale circRNA production, with important implications for RNA-based therapeutics and synthetic biology. The T4 td-PIE system is a promising platform for circular RNA synthesis, but the dynamic mechanism of the T4 td group I intron during circularization remains unclear. Now, cryo-EM structures of both the linear and circular forms of the T4 td intron are solved, revealing key conformational shifts essential for RNA circularization.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1281-1294"},"PeriodicalIF":44.6,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536471","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 : 2025-11-18DOI: 10.1038/s41929-025-01449-9
Thomas Götsch, Daniel Cruz, Patrick Zeller, Anna Rabe, Maik Dreyer, Nicolas Cosanne, Frank Girgsdies, Jasmin Allan, Michael Hävecker, Anna Efimenko, Mihaela Gorgoi, Sharif Najafishirtari, Malte Behrens, Robert Schlögl, Axel Knop-Gericke, Thomas Lunkenbein
Transition metal oxides are excellent catalysts for selective oxidation reactions, which are a prominent source of industrially relevant chemicals. However, these reactions suffer from multiple competing reaction pathways, limiting the selectivity. Thus, it is essential to gain an understanding of the underlying processes occurring on the catalyst that affect its performance. Here we synergistically combine operando X-ray spectroscopy and operando transmission electron microscopy to unravel a network of solid-state processes that controls the catalytic properties of Co3O4 in the oxidation of 2-propanol towards acetone. These include exsolution, diffusion and defect formation, which strongly distort the catalyst lattice at lower temperatures. Ultimately, they also lead to a maximum in acetone selectivity when the catalyst is trapped in a frustrated or metastable state at the onset of crystallization of the exsolved particles to CoO and void formation, which coincides with the maximum in surface cobalt oxidation state in the spinel. The notion that catalysts are static entities that barely change under operation is still prevalent although it is often not true. Here, a range of operando and in situ techniques reveals the dynamic nature of Co3O4 during the oxidation of 2-propanol to acetone, unveiling a network of interconnected solid-state processes, such as exsolution, diffusion or void formation, that govern the catalytic performance.
{"title":"Local solid-state processes adjust the selectivity in catalytic oxidation reactions on cobalt oxides","authors":"Thomas Götsch, Daniel Cruz, Patrick Zeller, Anna Rabe, Maik Dreyer, Nicolas Cosanne, Frank Girgsdies, Jasmin Allan, Michael Hävecker, Anna Efimenko, Mihaela Gorgoi, Sharif Najafishirtari, Malte Behrens, Robert Schlögl, Axel Knop-Gericke, Thomas Lunkenbein","doi":"10.1038/s41929-025-01449-9","DOIUrl":"10.1038/s41929-025-01449-9","url":null,"abstract":"Transition metal oxides are excellent catalysts for selective oxidation reactions, which are a prominent source of industrially relevant chemicals. However, these reactions suffer from multiple competing reaction pathways, limiting the selectivity. Thus, it is essential to gain an understanding of the underlying processes occurring on the catalyst that affect its performance. Here we synergistically combine operando X-ray spectroscopy and operando transmission electron microscopy to unravel a network of solid-state processes that controls the catalytic properties of Co3O4 in the oxidation of 2-propanol towards acetone. These include exsolution, diffusion and defect formation, which strongly distort the catalyst lattice at lower temperatures. Ultimately, they also lead to a maximum in acetone selectivity when the catalyst is trapped in a frustrated or metastable state at the onset of crystallization of the exsolved particles to CoO and void formation, which coincides with the maximum in surface cobalt oxidation state in the spinel. The notion that catalysts are static entities that barely change under operation is still prevalent although it is often not true. Here, a range of operando and in situ techniques reveals the dynamic nature of Co3O4 during the oxidation of 2-propanol to acetone, unveiling a network of interconnected solid-state processes, such as exsolution, diffusion or void formation, that govern the catalytic performance.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1314-1324"},"PeriodicalIF":44.6,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01449-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536705","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}
Substituted cyclohexanes are ubiquitous motifs in bioactive molecules. Thermodynamically disfavoured substituted cyclohexane scaffolds can significantly enhance both the biological activity and pharmacokinetic properties of potential drugs. However, achieving stereoselective cross-coupling for the synthesis of these structures with precise kinetic control remains a challenge. Here we present a modular reductive cross-coupling reaction that enables the stereoselective synthesis of thermodynamically disfavoured substituted cyclohexanes, employing simple alkenes as coupling partners. Mechanistically, the exceptional stereochemistry of this reaction is governed by a Heck-type migratory insertion step. The utility of this method is also demonstrated through the concise synthesis of bioactive molecules. Thermodynamically disfavoured substituted cyclohexane compounds often display superior physical and bioactive properties to their isomeric counterparts. Now their synthesis is achieved by Ni-catalysed coupling of substituted methylenecyclohexanes with electrophiles under kinetic control.
{"title":"A stereoselective reductive cross-coupling reaction with kinetic control","authors":"Zhenpeng Shen, Hongjin Shi, Yangyang Li, Xiangyu Zhang, Xiaotian Qi, Guoyin Yin","doi":"10.1038/s41929-025-01440-4","DOIUrl":"10.1038/s41929-025-01440-4","url":null,"abstract":"Substituted cyclohexanes are ubiquitous motifs in bioactive molecules. Thermodynamically disfavoured substituted cyclohexane scaffolds can significantly enhance both the biological activity and pharmacokinetic properties of potential drugs. However, achieving stereoselective cross-coupling for the synthesis of these structures with precise kinetic control remains a challenge. Here we present a modular reductive cross-coupling reaction that enables the stereoselective synthesis of thermodynamically disfavoured substituted cyclohexanes, employing simple alkenes as coupling partners. Mechanistically, the exceptional stereochemistry of this reaction is governed by a Heck-type migratory insertion step. The utility of this method is also demonstrated through the concise synthesis of bioactive molecules. Thermodynamically disfavoured substituted cyclohexane compounds often display superior physical and bioactive properties to their isomeric counterparts. Now their synthesis is achieved by Ni-catalysed coupling of substituted methylenecyclohexanes with electrophiles under kinetic control.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1241-1249"},"PeriodicalIF":44.6,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455582","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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