Pub Date : 2026-01-23DOI: 10.1038/s41557-025-02041-1
Kun Ho 'Kenny' Park, Jisook Park, Nils Frank, Hanwen Zhang, Peilin Tian, Yasmine Biddick, Fernanda Duarte, Edward A Anderson
The Strychnos alkaloids have long been regarded as landmark targets for chemical synthesis due to their captivating architectures and notorious biological properties. However, the design of approaches that access multiple family members in an asymmetric, concise and atom-economical fashion remains an important challenge. Here we show that thiophene S,S-dioxides (TDOs) offer a modular, rapid entry to Strychnos natural products via inverse electron demand Diels-Alder cascades. We demonstrate that exceptional levels of stereocontrol can be achieved in asymmetric TDO cycloadditions, affording tricyclic indolines of utility in medicinal chemistry research and enabling the stereoselective synthesis of eight Strychnos alkaloids by the shortest routes described so far, including a synthesis of the iconic family member brucine. Using a machine-learning approach, computational studies provide insight into the source of stereoinduction and reveal an intriguing and unexpected spontaneous cheletropic extrusion of SO2.
{"title":"Collective asymmetric synthesis of the Strychnos alkaloids via thiophene S,S-dioxide cycloadditions.","authors":"Kun Ho 'Kenny' Park, Jisook Park, Nils Frank, Hanwen Zhang, Peilin Tian, Yasmine Biddick, Fernanda Duarte, Edward A Anderson","doi":"10.1038/s41557-025-02041-1","DOIUrl":"https://doi.org/10.1038/s41557-025-02041-1","url":null,"abstract":"<p><p>The Strychnos alkaloids have long been regarded as landmark targets for chemical synthesis due to their captivating architectures and notorious biological properties. However, the design of approaches that access multiple family members in an asymmetric, concise and atom-economical fashion remains an important challenge. Here we show that thiophene S,S-dioxides (TDOs) offer a modular, rapid entry to Strychnos natural products via inverse electron demand Diels-Alder cascades. We demonstrate that exceptional levels of stereocontrol can be achieved in asymmetric TDO cycloadditions, affording tricyclic indolines of utility in medicinal chemistry research and enabling the stereoselective synthesis of eight Strychnos alkaloids by the shortest routes described so far, including a synthesis of the iconic family member brucine. Using a machine-learning approach, computational studies provide insight into the source of stereoinduction and reveal an intriguing and unexpected spontaneous cheletropic extrusion of SO<sub>2</sub>.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146041415","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 : 2026-01-23DOI: 10.1038/s41557-026-02066-0
{"title":"Engineering the electronic properties of DNA.","authors":"","doi":"10.1038/s41557-026-02066-0","DOIUrl":"https://doi.org/10.1038/s41557-026-02066-0","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"42 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034033","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 : 2026-01-21DOI: 10.1038/s41557-025-02055-9
Jiaming Ding, Sarah A. French, Christina A. Rivera, Arismel Tena Meza, Dominick C. Witkowski, K. N. Houk, Neil K. Garg
Alkenes typically have trigonal planar geometries at each terminus, with favourable σ- and π-bonding leading to a bond order of ~2. Here we consider unusual alkenes that possess an extreme form of geometric distortion, termed hyperpyramidalization. In a hyperpyramidalized alkene, geometries deviate remarkably from the typical trigonal planar alkene geometry, leading to weak π-bonding and abnormal alkene bond orders approaching 1.5. Cubene and 1,7-quadricyclene, first validated in 1988 and 1979, respectively, but overlooked for decades since, are the focus of the present study. We leverage their unusually weak π-bonds in cycloadditions, enabling the construction of complex scaffolds and access to previously unrealized chemical space. The origins of the unusually low bond orders were investigated using computational methods. These efforts are expected to prompt future studies of molecules that display hyperpyramidalization or atypical bond orders.
{"title":"Hyperpyramidalized alkenes with bond orders near 1.5 as synthetic building blocks","authors":"Jiaming Ding, Sarah A. French, Christina A. Rivera, Arismel Tena Meza, Dominick C. Witkowski, K. N. Houk, Neil K. Garg","doi":"10.1038/s41557-025-02055-9","DOIUrl":"https://doi.org/10.1038/s41557-025-02055-9","url":null,"abstract":"Alkenes typically have trigonal planar geometries at each terminus, with favourable σ- and π-bonding leading to a bond order of ~2. Here we consider unusual alkenes that possess an extreme form of geometric distortion, termed hyperpyramidalization. In a hyperpyramidalized alkene, geometries deviate remarkably from the typical trigonal planar alkene geometry, leading to weak π-bonding and abnormal alkene bond orders approaching 1.5. Cubene and 1,7-quadricyclene, first validated in 1988 and 1979, respectively, but overlooked for decades since, are the focus of the present study. We leverage their unusually weak π-bonds in cycloadditions, enabling the construction of complex scaffolds and access to previously unrealized chemical space. The origins of the unusually low bond orders were investigated using computational methods. These efforts are expected to prompt future studies of molecules that display hyperpyramidalization or atypical bond orders.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"53 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146006365","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}
Vinylene-linked two-dimensional (2D) conjugated covalent organic frameworks, or 2D poly(arylene vinylene)s (2D PAVs), are promising polymer semiconductors for (opto-)electronics, photocatalysis and electrochemistry. However, conventional solvothermal synthesis often produces 2D PAVs that are poorly crystalline or difficult to access. Here we introduce a Mannich-elimination strategy that converts 8 2D imine-covalent organic frameworks into 11 highly crystalline 2D PAVs though a reversible C=C bond formation mechanism enabling precise crystallization control. This versatile approach affords robust 2D PAVs with honeycomb, square or kagome lattices, specific surface area up to ∼2,000 m2 g-1 and lattice-mismatch tolerance up to 3.5%. High-resolution transmission electron microscopy and continuous rotation electron diffraction reveal molecular-level ordering in a 2-µm-sized triphenylbenzene-based single-crystalline 2D PAV. We demonstrate that crystallinity profoundly influences charge transport, with benzotrithiophene-based 2D PAVs exhibiting charge mobilities tenfold higher than their amorphous analogues or 2D polyimine precursors. This work establishes a general route to highly crystalline 2D conjugated polymer materials for robust applications.
{"title":"Towards single-crystalline two-dimensional poly(arylene vinylene) covalent organic frameworks.","authors":"Shaik Ghouse,Ziang Guo,Sergio Gámez-Valenzuela,David Mücke,Bowen Zhang,Lei Gao,Silvia Paasch,Yubin Fu,Chuanhui Huang,Chandrashekar Naisa,Eike Brunner,Mischa Bonn,M Carmen Ruiz Delgado,Junliang Sun,Ruqiang Zou,Ute Kaiser,Mingchao Wang,Xinliang Feng","doi":"10.1038/s41557-025-02048-8","DOIUrl":"https://doi.org/10.1038/s41557-025-02048-8","url":null,"abstract":"Vinylene-linked two-dimensional (2D) conjugated covalent organic frameworks, or 2D poly(arylene vinylene)s (2D PAVs), are promising polymer semiconductors for (opto-)electronics, photocatalysis and electrochemistry. However, conventional solvothermal synthesis often produces 2D PAVs that are poorly crystalline or difficult to access. Here we introduce a Mannich-elimination strategy that converts 8 2D imine-covalent organic frameworks into 11 highly crystalline 2D PAVs though a reversible C=C bond formation mechanism enabling precise crystallization control. This versatile approach affords robust 2D PAVs with honeycomb, square or kagome lattices, specific surface area up to ∼2,000 m2 g-1 and lattice-mismatch tolerance up to 3.5%. High-resolution transmission electron microscopy and continuous rotation electron diffraction reveal molecular-level ordering in a 2-µm-sized triphenylbenzene-based single-crystalline 2D PAV. We demonstrate that crystallinity profoundly influences charge transport, with benzotrithiophene-based 2D PAVs exhibiting charge mobilities tenfold higher than their amorphous analogues or 2D polyimine precursors. This work establishes a general route to highly crystalline 2D conjugated polymer materials for robust applications.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"6 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005145","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 : 2026-01-20DOI: 10.1038/s41557-025-02058-6
Simon K. Beaumont
Solid catalysts are typically optimized by changing their structure to control the strength of the adsorption bond. Now, magnetic spin-ordering offers an orthogonal energetic lever with which to enhance the otherwise sluggish kinetics of the ammonia oxidation reaction.
{"title":"Magnetism adds a dimension to ammonia oxidation electrocatalysts","authors":"Simon K. Beaumont","doi":"10.1038/s41557-025-02058-6","DOIUrl":"10.1038/s41557-025-02058-6","url":null,"abstract":"Solid catalysts are typically optimized by changing their structure to control the strength of the adsorption bond. Now, magnetic spin-ordering offers an orthogonal energetic lever with which to enhance the otherwise sluggish kinetics of the ammonia oxidation reaction.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"217-218"},"PeriodicalIF":20.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005146","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 : 2026-01-20DOI: 10.1038/s41557-025-02035-z
Bin Cai,Andjela Brnovic,Mariia V Pavliuk,Leif Hammarström,Lars Kloo,Sarah A Barnett,Haining Tian
Photocatalysis offers a promising approach for renewable energy conversion and storage, but short lifetimes of charge-separated states in photocatalysts due to charge recombination limit its utility. Here we report an organic molecule with an acceptor-donor-acceptor configuration that can self assemble into highly crystalline nanoparticles. Transient absorption spectroscopy reveals that these crystalline assemblies can induce an ultra-long-lived charge-separated state of up to 1.2 s, attributed to initial symmetry-breaking charge separation, followed by charge hopping across closely packed molecules. These self-assembled nanoparticles have an impressive photocatalytic H2 evolution rate of 126 mmol g-1 h-1 with an external quantum efficiency of 12% at 550 nm under optimized conditions. This system shows a remarkable stability with 220 million turnover numbers (per particle) over the 77 h of operation. These findings suggest that rational design of organic molecules and their aggregates is vital for improving light-induced charge separation and for developing highly efficient, stable and scalable organic photocatalysts.
{"title":"Organic crystalline nanoparticles with a long-lived charge-separated state for efficient photocatalytic hydrogen production.","authors":"Bin Cai,Andjela Brnovic,Mariia V Pavliuk,Leif Hammarström,Lars Kloo,Sarah A Barnett,Haining Tian","doi":"10.1038/s41557-025-02035-z","DOIUrl":"https://doi.org/10.1038/s41557-025-02035-z","url":null,"abstract":"Photocatalysis offers a promising approach for renewable energy conversion and storage, but short lifetimes of charge-separated states in photocatalysts due to charge recombination limit its utility. Here we report an organic molecule with an acceptor-donor-acceptor configuration that can self assemble into highly crystalline nanoparticles. Transient absorption spectroscopy reveals that these crystalline assemblies can induce an ultra-long-lived charge-separated state of up to 1.2 s, attributed to initial symmetry-breaking charge separation, followed by charge hopping across closely packed molecules. These self-assembled nanoparticles have an impressive photocatalytic H2 evolution rate of 126 mmol g-1 h-1 with an external quantum efficiency of 12% at 550 nm under optimized conditions. This system shows a remarkable stability with 220 million turnover numbers (per particle) over the 77 h of operation. These findings suggest that rational design of organic molecules and their aggregates is vital for improving light-induced charge separation and for developing highly efficient, stable and scalable organic photocatalysts.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"275 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005147","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 : 2026-01-20DOI: 10.1038/s41557-025-02057-7
Bidushi Sarkar,Rameshwar L Kumawat,Peiyuan Ma,Ke-Hsin Wang,Matin Mohebi,George C Schatz,Chibueze V Amanchukwu
Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. We show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C2-C6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C-F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F- as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.
{"title":"Lithium metal-mediated electrochemical reduction of per- and poly-fluoroalkyl substances.","authors":"Bidushi Sarkar,Rameshwar L Kumawat,Peiyuan Ma,Ke-Hsin Wang,Matin Mohebi,George C Schatz,Chibueze V Amanchukwu","doi":"10.1038/s41557-025-02057-7","DOIUrl":"https://doi.org/10.1038/s41557-025-02057-7","url":null,"abstract":"Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. We show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C2-C6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C-F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F- as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"41 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005565","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 : 2026-01-19DOI: 10.1038/s41557-025-02059-5
Xinyuan Zhang (, ), Hong Jin Fan (, )
Unlocking the full potential of zinc–iodine batteries requires the prevention of side effects arising from reactive polyiodide intermediates. Now, a synergistic redox-coupling strategy confines the conversion reaction within the cathode, enabling shuttle-free batteries with enhanced reversibility and increased energy density.
{"title":"Taming polyiodide flow with electroactive mediators","authors":"Xinyuan Zhang \u0000 (, ), Hong Jin Fan \u0000 (, )","doi":"10.1038/s41557-025-02059-5","DOIUrl":"10.1038/s41557-025-02059-5","url":null,"abstract":"Unlocking the full potential of zinc–iodine batteries requires the prevention of side effects arising from reactive polyiodide intermediates. Now, a synergistic redox-coupling strategy confines the conversion reaction within the cathode, enabling shuttle-free batteries with enhanced reversibility and increased energy density.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"219-220"},"PeriodicalIF":20.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146003737","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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