Pub Date : 2026-01-30DOI: 10.1038/s44160-025-00982-6
{"title":"Isolation of an isodiazomethyl anion as a nitrene synthon","authors":"","doi":"10.1038/s44160-025-00982-6","DOIUrl":"https://doi.org/10.1038/s44160-025-00982-6","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098118","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 : 2026-01-30DOI: 10.1038/s44160-025-00979-1
Jing Gong, Qian Wang, Jieping Zhu
In sharp contrast to 1,2-rearrangement, a concerted 1,3-alkyl shift is generally not feasible due to the antiaromatic 4π Hückel transition state and geometric strain. Existing stepwise approaches, which involve radical and organometallic intermediates, often lead to racemization of the migrating atom’s stereocentre and suffer from the highly competitive β-hydride elimination reaction. Theoretically, two consecutive 1,2-shifts could produce the same product as a direct 1,3-migration. Specifically, two scenarios are possible: two successive migrations of the same atom or sequential migrations of two different bonding atoms. Here we report the realization of this strategy by integrating a palladium-catalysed semi-pinacol rearrangement with a 1,2-C/Pd(IV) dyotropic rearrangement. We demonstrate that two distinct 1,3-shift products can be selectively obtained by controlling the conformation of the Pd(II) intermediate, which can in turn be modulated by the metal’s supporting ligand. A key feature of this methodology is that the absolute configuration of the migrating group is retained, an outcome unachievable with existing strategies.
与1,2-重排形成鲜明对比的是，由于反芳香的4π h ckel过渡态和几何应变，一致的1,3-烷基移位通常是不可行的。现有的分步方法，涉及自由基和有机金属中间体，往往导致迁移原子的立体中心外消旋，并遭受高度竞争的β-氢化物消除反应。理论上，两个连续的1,2班次可以产生与直接1,3迁移相同的产品。具体来说，有两种情况是可能的：同一原子的两次连续迁移或两个不同键合原子的连续迁移。在这里，我们通过整合钯催化的半蒎醇重排和1,2- c /Pd（IV）各向异性重排来实现这一策略。我们证明，通过控制Pd（II）中间体的构象，可以选择性地获得两种不同的1,3移位产物，而Pd（II）中间体的构象又可以被金属的支撑配体调节。该方法的一个关键特征是迁移群体的绝对配置被保留，这是现有策略无法实现的结果。
{"title":"Concerted 1,3-migration through regiodivergent consecutive 1,2-rearrangements using palladium catalysis","authors":"Jing Gong, Qian Wang, Jieping Zhu","doi":"10.1038/s44160-025-00979-1","DOIUrl":"https://doi.org/10.1038/s44160-025-00979-1","url":null,"abstract":"In sharp contrast to 1,2-rearrangement, a concerted 1,3-alkyl shift is generally not feasible due to the antiaromatic 4π Hückel transition state and geometric strain. Existing stepwise approaches, which involve radical and organometallic intermediates, often lead to racemization of the migrating atom’s stereocentre and suffer from the highly competitive β-hydride elimination reaction. Theoretically, two consecutive 1,2-shifts could produce the same product as a direct 1,3-migration. Specifically, two scenarios are possible: two successive migrations of the same atom or sequential migrations of two different bonding atoms. Here we report the realization of this strategy by integrating a palladium-catalysed semi-pinacol rearrangement with a 1,2-C/Pd(IV) dyotropic rearrangement. We demonstrate that two distinct 1,3-shift products can be selectively obtained by controlling the conformation of the Pd(II) intermediate, which can in turn be modulated by the metal’s supporting ligand. A key feature of this methodology is that the absolute configuration of the migrating group is retained, an outcome unachievable with existing strategies.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098116","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 : 2026-01-30DOI: 10.1038/s44160-025-00974-6
{"title":"Synthesis of fused pyridines through photothermal cascade activation of arylhydrazines","authors":"","doi":"10.1038/s44160-025-00974-6","DOIUrl":"https://doi.org/10.1038/s44160-025-00974-6","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"232 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098115","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 : 2026-01-30DOI: 10.1038/s44160-025-00976-4
Kun Li, Yin Zeng, Kai-Hang Li, Yifan Yang, Jinhui Shen, Huifeng Guo, Yingfei Tan, Jing-Jing Guo, Anhua Hu
The skeletal remodelling of benzene has been widely acknowledged as an attractive yet challenging approach for utilizing the extensive array of aromatic compounds. A primary challenge lies not only in overcoming the high activation barrier associated with the dearomatization step but also in achieving site-selective skeletal modifications within a single operational sequence. Here we present a photothermal cascade activation mode that unlocks the photoactivation reactivity of the transiently generated light-absorbing intermediate formed during interrupted Fischer indolization. Complementary to arene ring expansion methodologies, this protocol offers a practical ring contraction approach for the modular synthesis of fused pyridines with good functional group tolerance and predictable regioselectivity. This strategy is expected to broaden the chemical landscape for the design of innovative photochemical reactions.
{"title":"Photoinduced benzene ring contraction of arylhydrazines for the synthesis of fused pyridines","authors":"Kun Li, Yin Zeng, Kai-Hang Li, Yifan Yang, Jinhui Shen, Huifeng Guo, Yingfei Tan, Jing-Jing Guo, Anhua Hu","doi":"10.1038/s44160-025-00976-4","DOIUrl":"https://doi.org/10.1038/s44160-025-00976-4","url":null,"abstract":"The skeletal remodelling of benzene has been widely acknowledged as an attractive yet challenging approach for utilizing the extensive array of aromatic compounds. A primary challenge lies not only in overcoming the high activation barrier associated with the dearomatization step but also in achieving site-selective skeletal modifications within a single operational sequence. Here we present a photothermal cascade activation mode that unlocks the photoactivation reactivity of the transiently generated light-absorbing intermediate formed during interrupted Fischer indolization. Complementary to arene ring expansion methodologies, this protocol offers a practical ring contraction approach for the modular synthesis of fused pyridines with good functional group tolerance and predictable regioselectivity. This strategy is expected to broaden the chemical landscape for the design of innovative photochemical reactions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"82 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098117","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 : 2026-01-27DOI: 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}
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