Pub Date : 2026-01-27DOI: 10.1038/s44160-025-00981-7
Hongyu Wang, Jiancheng Li, Liu Leo Liu
Basic organic motifs built from carbon and nitrogen are long-established cornerstones of synthetic chemistry. Yet, it has become increasingly challenging to design new three-atom C/N assemblies with uncharted structures and properties. While organic azides (R–N3, R = organic group) and diazomethyl anions (R–CN2)− have long served as versatile synthetic platforms, their isoelectronic isodiazomethyl anion counterparts (R–NNC)− have remained elusive in the absence of transition-metal stabilization. Here we report the isolation and structural characterization of a metal-free isodiazomethyl anion. This boryl-isodiazomethyl anion features a bent eneyne-type B=N–N≡C scaffold exhibiting pronounced charge separation and a highly nucleophilic, boron-bound nitrogen centre. This characteristic enables a rare, concerted CN−/CO exchange at the nitrogen atom to yield a boryl-isocyanate, as well as easy metathesis reactions with C=O, C=S and C=N bonds. Quantum chemical calculations further reveal that the ‘U-turn’ migration of the terminal NC fragment is pivotal in driving the observed metathesis transformations.
{"title":"A crystalline isodiazomethyl anion","authors":"Hongyu Wang, Jiancheng Li, Liu Leo Liu","doi":"10.1038/s44160-025-00981-7","DOIUrl":"https://doi.org/10.1038/s44160-025-00981-7","url":null,"abstract":"Basic organic motifs built from carbon and nitrogen are long-established cornerstones of synthetic chemistry. Yet, it has become increasingly challenging to design new three-atom C/N assemblies with uncharted structures and properties. While organic azides (R–N3, R = organic group) and diazomethyl anions (R–CN2)− have long served as versatile synthetic platforms, their isoelectronic isodiazomethyl anion counterparts (R–NNC)− have remained elusive in the absence of transition-metal stabilization. Here we report the isolation and structural characterization of a metal-free isodiazomethyl anion. This boryl-isodiazomethyl anion features a bent eneyne-type B=N–N≡C scaffold exhibiting pronounced charge separation and a highly nucleophilic, boron-bound nitrogen centre. This characteristic enables a rare, concerted CN−/CO exchange at the nitrogen atom to yield a boryl-isocyanate, as well as easy metathesis reactions with C=O, C=S and C=N bonds. Quantum chemical calculations further reveal that the ‘U-turn’ migration of the terminal NC fragment is pivotal in driving the observed metathesis transformations.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"78 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Functional mesoporous nanomaterials (FMNs), combining the advantages of mesoporosity and nanoscale effects, have attracted interest owing to their wide-ranging applications. Recent advances demonstrate that the nanoemulsion modular assembly method is a scalable, efficient and versatile platform for synthesizing FMNs in high yields, surpassing traditional templating methods in terms of the controllability in pore size, structure and morphology. Here we present the fundamentals and recent progress in nanoemulsion modular assembly for the design of diverse FMNs, including mesoporous polymers, carbons, silicas, organosilicas, metal–organic frameworks and their heterostructures. We first discuss representative nanoemulsion components and the modular assembly concept, and highlight key distinctions from traditional strategies. Next we present the structural control over nanoemulsions, discussing the underlying mechanisms that govern the diversity of FMNs. Subsequently, we summarize their applications in energy storage, catalysis, sensing and biomedicine. Finally, we outline unresolved challenges and future opportunities, underscoring the possibilities of nanoemulsion-based assembly strategies in advancing next-generation functional nanomaterials. Nanoemulsion modular assembly is emerging as a versatile strategy for synthesizing diverse functional mesoporous nanomaterials. This Review highlights the capabilities of nanoemulsion modular assembly for precise control over pore size, structure, composition and morphology, as well as discussing possible applications of functional mesoporous nanomaterials.
{"title":"Nanoemulsion modular assembly for the synthesis of functional mesoporous nanomaterials","authors":"Liang Peng, Huarong Peng, Yongjiu Yuan, Yuxin Song, Xiao Yang, Pengcheng Sun, Yingying Yin, Steven Wang, Zhengxiao Guo, Dongyuan Zhao, Zuankai Wang","doi":"10.1038/s44160-025-00973-7","DOIUrl":"10.1038/s44160-025-00973-7","url":null,"abstract":"Functional mesoporous nanomaterials (FMNs), combining the advantages of mesoporosity and nanoscale effects, have attracted interest owing to their wide-ranging applications. Recent advances demonstrate that the nanoemulsion modular assembly method is a scalable, efficient and versatile platform for synthesizing FMNs in high yields, surpassing traditional templating methods in terms of the controllability in pore size, structure and morphology. Here we present the fundamentals and recent progress in nanoemulsion modular assembly for the design of diverse FMNs, including mesoporous polymers, carbons, silicas, organosilicas, metal–organic frameworks and their heterostructures. We first discuss representative nanoemulsion components and the modular assembly concept, and highlight key distinctions from traditional strategies. Next we present the structural control over nanoemulsions, discussing the underlying mechanisms that govern the diversity of FMNs. Subsequently, we summarize their applications in energy storage, catalysis, sensing and biomedicine. Finally, we outline unresolved challenges and future opportunities, underscoring the possibilities of nanoemulsion-based assembly strategies in advancing next-generation functional nanomaterials. Nanoemulsion modular assembly is emerging as a versatile strategy for synthesizing diverse functional mesoporous nanomaterials. This Review highlights the capabilities of nanoemulsion modular assembly for precise control over pore size, structure, composition and morphology, as well as discussing possible applications of functional mesoporous nanomaterials.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"162-179"},"PeriodicalIF":20.0,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146155307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1038/s44160-025-00968-4
Jingcheng Hu, Jiayu Hu, Yatao Wang, Chen Zeng, Heng Zhang, Zhenwei Wei, Wu Li, Hong Yi, Aiwen Lei
Sulfur dioxide (SO2) is a widespread industrial pollutant from fossil fuel combustion and metal smelting that causes serious environmental and health concerns. Converting SO2 into valuable chemicals provides a sustainable solution for emission mitigation and resource use. Here we show a paired electrolysis strategy that directly transforms SO2 into cyclic sulfite esters—high-value organosulfur intermediates widely used in organic synthesis and as precursors for functional materials—under mild conditions. SO2 is reduced at the cathode to elemental sulfur, which then undergoes anodic oxidation and couples with alcohols to form five-membered, six-membered and seven-membered cyclic sulfite esters. Mechanistic studies reveal key sulfur-containing intermediates and elucidate the critical redox pathways. This method efficiently converts even low concentrations of SO2, including simulated industrial flue gas, demonstrating practical applicability. The strategy provides a versatile and environmentally friendly platform for green organosulfur synthesis and pollutant valorization, opening new avenues for sustainable chemical manufacturing.
{"title":"Parallel paired electrolysis of industrial exhaust SO2 and diols for value-added sulfite esters synthesis","authors":"Jingcheng Hu, Jiayu Hu, Yatao Wang, Chen Zeng, Heng Zhang, Zhenwei Wei, Wu Li, Hong Yi, Aiwen Lei","doi":"10.1038/s44160-025-00968-4","DOIUrl":"https://doi.org/10.1038/s44160-025-00968-4","url":null,"abstract":"Sulfur dioxide (SO2) is a widespread industrial pollutant from fossil fuel combustion and metal smelting that causes serious environmental and health concerns. Converting SO2 into valuable chemicals provides a sustainable solution for emission mitigation and resource use. Here we show a paired electrolysis strategy that directly transforms SO2 into cyclic sulfite esters—high-value organosulfur intermediates widely used in organic synthesis and as precursors for functional materials—under mild conditions. SO2 is reduced at the cathode to elemental sulfur, which then undergoes anodic oxidation and couples with alcohols to form five-membered, six-membered and seven-membered cyclic sulfite esters. Mechanistic studies reveal key sulfur-containing intermediates and elucidate the critical redox pathways. This method efficiently converts even low concentrations of SO2, including simulated industrial flue gas, demonstrating practical applicability. The strategy provides a versatile and environmentally friendly platform for green organosulfur synthesis and pollutant valorization, opening new avenues for sustainable chemical manufacturing.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1038/s44160-025-00954-w
Shuai-Liang Yang, Liang Qiao, Bingyu Liu, Rui Yao, Xiao Wang, Wei Gong, Yan Liu, Jinqiao Dong, Anthony P. Davis, Yong Cui
Chiral mechanically interlocked molecules provide a promising platform for enantioselective recognition and asymmetric catalysis, enabled by their unique combination of topological complexity and stereochemical control. Despite recent advances, the rational construction of higher-order chiral interlocked architectures such as molecular knots and links remains a synthetic challenge. Moreover, the influence of molecular chirality on the formation of such topological structures, and the resulting functional consequences, has been largely unexplored. Here we report an amino-acid-encoded assembly strategy as a general approach for the synthesis of programmable Solomon links (doubly interlocked [2]catenanes) featuring multiple levels of structural chirality. By leveraging the stereochemical configurations of amino acids to introduce chiral bias and encode structural information, we demonstrate that the assembly process preferentially follows a homochiral assembly pathway over non-chiral or heterochiral alternatives, resulting in a library of chiral Solomon links with tunable cavity size and shape, generated in a single step with high efficiency. These interlocked molecules exhibit exceptional chiral amplification (∼350-fold increase) and outstanding binding affinity and enantioselectivity for peptides, with practical applications in interleukin-6 detection (∼12 nM sensitivity). This template-free synthetic approach paves the way to the custom design of chiral interlocked architectures and materials with tailored properties.
{"title":"Amino-acid-encoded assembly of programmable chiral Solomon links","authors":"Shuai-Liang Yang, Liang Qiao, Bingyu Liu, Rui Yao, Xiao Wang, Wei Gong, Yan Liu, Jinqiao Dong, Anthony P. Davis, Yong Cui","doi":"10.1038/s44160-025-00954-w","DOIUrl":"https://doi.org/10.1038/s44160-025-00954-w","url":null,"abstract":"Chiral mechanically interlocked molecules provide a promising platform for enantioselective recognition and asymmetric catalysis, enabled by their unique combination of topological complexity and stereochemical control. Despite recent advances, the rational construction of higher-order chiral interlocked architectures such as molecular knots and links remains a synthetic challenge. Moreover, the influence of molecular chirality on the formation of such topological structures, and the resulting functional consequences, has been largely unexplored. Here we report an amino-acid-encoded assembly strategy as a general approach for the synthesis of programmable Solomon links (doubly interlocked [2]catenanes) featuring multiple levels of structural chirality. By leveraging the stereochemical configurations of amino acids to introduce chiral bias and encode structural information, we demonstrate that the assembly process preferentially follows a homochiral assembly pathway over non-chiral or heterochiral alternatives, resulting in a library of chiral Solomon links with tunable cavity size and shape, generated in a single step with high efficiency. These interlocked molecules exhibit exceptional chiral amplification (∼350-fold increase) and outstanding binding affinity and enantioselectivity for peptides, with practical applications in interleukin-6 detection (∼12 nM sensitivity). This template-free synthetic approach paves the way to the custom design of chiral interlocked architectures and materials with tailored properties.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"56 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis covered in 2025","authors":"","doi":"10.1038/s44160-025-00972-8","DOIUrl":"10.1038/s44160-025-00972-8","url":null,"abstract":"In this Editorial, we reflect on some of the striking covers that Nature Synthesis published in 2025 and highlight the research they represent.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"1-1"},"PeriodicalIF":20.0,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00972-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145958183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Asymmetric addition to unsaturated double bonds provides an efficient strategy for the synthesis of optically active molecules. Despite advances over the past decades, achieving highly enantioselective transformations of purely alkyl-substituted 1,1-dialkylethenes has remained a challenge, particularly when involving open-shell radical intermediates. Here we present a cobalt-catalysed asymmetric radical hydroalkylation of 1,1-dialkyl-substituted alkenes with unactivated alkyl electrophiles, facilitating the formation of C(sp3)–C(sp3) bonds with simultaneous construction of traditionally unaccessible fully alkyl-substituted chiral tertiary carbon centres attaching substituents possessing similar steric and electronic properties. This enantioselective control does not rely on the assistance of heteroatoms or aryl functional groups as is often required in established approaches. Mechanistic studies indicate that the stereoselectivity primarily arises from the dispersion effect between catalyst and substrate, thereby avoiding substrate-specific constraints.
{"title":"Catalytic asymmetric hydroalkylation of 1,1-dialkyl-substituted alkenes with unactivated alkyl electrophiles","authors":"Shucheng Ma, Lihan Zhu, Jianjun Yin, Lianghua Wang, Xiuping Yuan, Simin Wang, Dazhen Shi, Qian Zhang, Tao Xiong","doi":"10.1038/s44160-025-00971-9","DOIUrl":"https://doi.org/10.1038/s44160-025-00971-9","url":null,"abstract":"Asymmetric addition to unsaturated double bonds provides an efficient strategy for the synthesis of optically active molecules. Despite advances over the past decades, achieving highly enantioselective transformations of purely alkyl-substituted 1,1-dialkylethenes has remained a challenge, particularly when involving open-shell radical intermediates. Here we present a cobalt-catalysed asymmetric radical hydroalkylation of 1,1-dialkyl-substituted alkenes with unactivated alkyl electrophiles, facilitating the formation of C(sp3)–C(sp3) bonds with simultaneous construction of traditionally unaccessible fully alkyl-substituted chiral tertiary carbon centres attaching substituents possessing similar steric and electronic properties. This enantioselective control does not rely on the assistance of heteroatoms or aryl functional groups as is often required in established approaches. Mechanistic studies indicate that the stereoselectivity primarily arises from the dispersion effect between catalyst and substrate, thereby avoiding substrate-specific constraints.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-06DOI: 10.1038/s44160-025-00965-7
Xu-Sheng Du, Pei-Pei Meng, Rui Xiong, Yu-Ting Liu, Feng-Qi Ren, Kun Liu, Zhe Zheng, Xin-Ao Mao, Kang Cai, Dong-Sheng Guo, Jonathan L. Sessler, Chunju Li
{"title":"Customized cycloparaphenylene skeletons prepared via the intramolecular coupling of extended biphen[n]arenes","authors":"Xu-Sheng Du, Pei-Pei Meng, Rui Xiong, Yu-Ting Liu, Feng-Qi Ren, Kun Liu, Zhe Zheng, Xin-Ao Mao, Kang Cai, Dong-Sheng Guo, Jonathan L. Sessler, Chunju Li","doi":"10.1038/s44160-025-00965-7","DOIUrl":"https://doi.org/10.1038/s44160-025-00965-7","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"82 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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