{"title":"Divergent synthesis of N heterocycles from carbocycles enabled by electrochemical nitrogen atom insertion","authors":"Guo-Quan Sun, Xiyan Wang, Rui Hu, Weidong Rao, Yu Zhao, Ming Joo Koh","doi":"10.1038/s44160-025-00945-x","DOIUrl":"https://doi.org/10.1038/s44160-025-00945-x","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771364","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 : 2025-12-16DOI: 10.1038/s44160-025-00925-1
Yilin Cao, Warabhorn Rodphon, Turki M. Alturaifi, Al Vicente Riano D. Lisboa, Zhouyang Ren, Job J. C. Struijs, Hui-Qi Ni, Taras Savchuk, Richard P. Loach, Shouliang Yang, Indrawan J. McAlpine, Donna G. Blackmond, Pavel K. Mykhailiuk, Peng Liu, K. Barry Sharpless, Keary M. Engle
Here we present the ambiphilic reactivity of alkyl sulfonyl fluorides in the stereoselective synthesis of diverse cyclopropanes from olefins, under palladium(II) catalysis. The sulfonyl fluoride functionality serves as both an acidifying group and an internal oxidant within the ambiphile, enabling successive carbopalladation and oxidative addition steps in the catalytic cycle, respectively. The transformation grants access to cis -substituted cyclopropanes and exhibits broad compatibility with various alkyl sulfonyl fluorides, including those bearing –CN, –CO 2 R, isoxazolyl, pyrazolyl and aryl groups. With internal alkene substrates, 1,2,3-trisubstituted cyclopropanes that are otherwise challenging to synthesize are formed in good-to-moderate yields and predictable diastereoselectivity. Detailed mechanistic insights from reaction progress kinetic analysis and density functional theory calculations reveal that the S N 2-type C–SO 2 F oxidative addition is the turnover-limiting and diastereoselectivity-determining step.
{"title":"Alkyl sulfonyl fluorides as ambiphiles in the stereoselective palladium(II)-catalysed cyclopropanation of unactivated alkenes","authors":"Yilin Cao, Warabhorn Rodphon, Turki M. Alturaifi, Al Vicente Riano D. Lisboa, Zhouyang Ren, Job J. C. Struijs, Hui-Qi Ni, Taras Savchuk, Richard P. Loach, Shouliang Yang, Indrawan J. McAlpine, Donna G. Blackmond, Pavel K. Mykhailiuk, Peng Liu, K. Barry Sharpless, Keary M. Engle","doi":"10.1038/s44160-025-00925-1","DOIUrl":"https://doi.org/10.1038/s44160-025-00925-1","url":null,"abstract":"Here we present the ambiphilic reactivity of alkyl sulfonyl fluorides in the stereoselective synthesis of diverse cyclopropanes from olefins, under palladium(II) catalysis. The sulfonyl fluoride functionality serves as both an acidifying group and an internal oxidant within the ambiphile, enabling successive carbopalladation and oxidative addition steps in the catalytic cycle, respectively. The transformation grants access to <jats:italic>cis</jats:italic> -substituted cyclopropanes and exhibits broad compatibility with various alkyl sulfonyl fluorides, including those bearing –CN, –CO <jats:sub>2</jats:sub> R, isoxazolyl, pyrazolyl and aryl groups. With internal alkene substrates, 1,2,3-trisubstituted cyclopropanes that are otherwise challenging to synthesize are formed in good-to-moderate yields and predictable diastereoselectivity. Detailed mechanistic insights from reaction progress kinetic analysis and density functional theory calculations reveal that the S <jats:sub>N</jats:sub> 2-type C–SO <jats:sub>2</jats:sub> F oxidative addition is the turnover-limiting and diastereoselectivity-determining step.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"43 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771135","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}
Sodium-ion batteries have been attracting extensive attention in both academic and industrial fields. However, the lack of large-area and ultrathin sodium (Na) metal foil hinders basic research on and commercialization of energy-dense Na-ion batteries. Here we successfully fabricated a metre-length, ultrathin (≤50 μm), mechanically strengthened Na metal foil by a roll-to-roll calendaring process with interfacial lubrication and functional modification. By developing self-lubricating polydimethylsiloxane as the multifunctional agent, the poor processibility of metallic Na is addressed by forming a mechanically strong interface as well as a surface lubricant film during rolling. Furthermore, polydimethylsiloxane-derived (Si–O)n-Na interphases can guide Na+-ion interfacial diffusion and enable a robust solid electrolyte interphase. Consequently, the large-area ultrathin Na foil exhibits a stable electrode potential and stripping capacity, as well as prolonged lifespan compared with bare Na anodes. This approach enables the realization of amp-hour-level Na metal pouch cells under a low negative-to-positive capacity ratio of 1.9, showing an energy density of 180.2 Wh kg−1. This scalable ultrathin Na foil establishes a materials foundation for fundamental studies on Na-ion batteries and the potential manufacture of high-energy-density Na metal batteries.
{"title":"Scalable ultrathin sodium metal anodes","authors":"Mengyao Tang, Shuai Dong, Ke Yue, Jinhui Zhao, Weiping Li, Xuefeng Wang, Peng Chen, Ruizhi Liu, Rui Wen, Shuangyu Song, Yujing Liu, Jianwei Nai, Jiawei Wang, Qiaonan Zhu, Liwei Cheng, Hao Lan, Liqiang Wu, Bin Zhou, Daojun Yang, Xinyong Tao, Lin Guo, Hua Wang","doi":"10.1038/s44160-025-00934-0","DOIUrl":"https://doi.org/10.1038/s44160-025-00934-0","url":null,"abstract":"Sodium-ion batteries have been attracting extensive attention in both academic and industrial fields. However, the lack of large-area and ultrathin sodium (Na) metal foil hinders basic research on and commercialization of energy-dense Na-ion batteries. Here we successfully fabricated a metre-length, ultrathin (≤50 μm), mechanically strengthened Na metal foil by a roll-to-roll calendaring process with interfacial lubrication and functional modification. By developing self-lubricating polydimethylsiloxane as the multifunctional agent, the poor processibility of metallic Na is addressed by forming a mechanically strong interface as well as a surface lubricant film during rolling. Furthermore, polydimethylsiloxane-derived (Si–O)n-Na interphases can guide Na+-ion interfacial diffusion and enable a robust solid electrolyte interphase. Consequently, the large-area ultrathin Na foil exhibits a stable electrode potential and stripping capacity, as well as prolonged lifespan compared with bare Na anodes. This approach enables the realization of amp-hour-level Na metal pouch cells under a low negative-to-positive capacity ratio of 1.9, showing an energy density of 180.2 Wh kg−1. This scalable ultrathin Na foil establishes a materials foundation for fundamental studies on Na-ion batteries and the potential manufacture of high-energy-density Na metal batteries.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"139 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717369","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 : 2025-12-09DOI: 10.1038/s44160-025-00962-w
Eric J. Piechota
{"title":"Heck-type reactions with bismuth photocatalysts","authors":"Eric J. Piechota","doi":"10.1038/s44160-025-00962-w","DOIUrl":"10.1038/s44160-025-00962-w","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 12","pages":"1475-1475"},"PeriodicalIF":20.0,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145706650","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 : 2025-12-08DOI: 10.1038/s44160-025-00949-7
Keisuke Kondo, Matthew Lowe, Nathan Davison, Paul G. Waddell, Roly J. Armstrong, Erli Lu, Koji Kubota, Hajime Ito
Organometallic reagents are essential in organic synthesis, with organolithium compounds being most widely used. However, as lithium becomes less abundant and increasingly expensive, organosodium compounds have emerged as promising alternatives, but their use in organic synthesis is limited by their poor solubility in organic solvents, the need for pre-activated sodium sources and the necessity for highly anhydrous conditions. Here we report a mechanochemical protocol for the direct generation of organosodium compounds from cheap and shelf-stable sodium lumps and readily available organic halides under bulk, solvent-free conditions. These reactions generate an array of organosodium compounds in minutes, without special precautions against moisture or temperature control. These nucleophiles can be used directly for one-pot nucleophilic addition reactions with electrophiles and nickel-catalysed cross-coupling reactions. Furthermore, this mechanochemical approach enables the sodiation of inert C–F bonds in organic fluorides. This method is anticipated to drive progress in sodium-based synthetic chemistry.
{"title":"Mechanochemical synthesis of organosodium compounds through direct sodiation of organic halides","authors":"Keisuke Kondo, Matthew Lowe, Nathan Davison, Paul G. Waddell, Roly J. Armstrong, Erli Lu, Koji Kubota, Hajime Ito","doi":"10.1038/s44160-025-00949-7","DOIUrl":"https://doi.org/10.1038/s44160-025-00949-7","url":null,"abstract":"Organometallic reagents are essential in organic synthesis, with organolithium compounds being most widely used. However, as lithium becomes less abundant and increasingly expensive, organosodium compounds have emerged as promising alternatives, but their use in organic synthesis is limited by their poor solubility in organic solvents, the need for pre-activated sodium sources and the necessity for highly anhydrous conditions. Here we report a mechanochemical protocol for the direct generation of organosodium compounds from cheap and shelf-stable sodium lumps and readily available organic halides under bulk, solvent-free conditions. These reactions generate an array of organosodium compounds in minutes, without special precautions against moisture or temperature control. These nucleophiles can be used directly for one-pot nucleophilic addition reactions with electrophiles and nickel-catalysed cross-coupling reactions. Furthermore, this mechanochemical approach enables the sodiation of inert C–F bonds in organic fluorides. This method is anticipated to drive progress in sodium-based synthetic chemistry.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711519","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 : 2025-12-05DOI: 10.1038/s44160-025-00936-y
Weihua Guo, Zihao Li, Libei Huang, Ma Qian, James M. Tour, Ruquan Ye
Laser technology has revolutionized industrial manufacturing by offering localized high energy, precise spatial resolution and seamless automation. Compared with traditional thermal processes, laser-assisted manufacturing integrates materials synthesis and structural design, thereby reducing waste and enhancing productivity. The rapid kinetics and transient behaviour of laser processes enable control over phase transitions, heterostructure design, defect engineering, nucleation, compositional variations, recrystallization and amorphization, producing materials with interesting properties. Here we examine atomic- and nanoscale control in laser-assisted materials manufacturing. We discuss the laser processing synthesis and resultant properties of materials including metals, perovskites, graphene and other inorganic materials. The efficacy of atomic- and nanoscale modulation by laser processing is demonstrated by improved performance in diverse domains, including catalysis, mechanical reinforcement, electronics or optoelectronics, and drug screening. By emphasizing atomic-scale perspectives, this Review offers understanding of laser-assisted materials manufacturing while inspiring materials development. Laser technology offers high energy, precise spatial resolution and seamless automation for materials synthesis and device fabrication. This Review highlights laser-assisted materials engineering at the atomic and nanoscales and examines the laser-assisted discovery of materials with interesting properties and applications.
{"title":"Laser-assisted materials engineering at the atomic and nanoscales","authors":"Weihua Guo, Zihao Li, Libei Huang, Ma Qian, James M. Tour, Ruquan Ye","doi":"10.1038/s44160-025-00936-y","DOIUrl":"10.1038/s44160-025-00936-y","url":null,"abstract":"Laser technology has revolutionized industrial manufacturing by offering localized high energy, precise spatial resolution and seamless automation. Compared with traditional thermal processes, laser-assisted manufacturing integrates materials synthesis and structural design, thereby reducing waste and enhancing productivity. The rapid kinetics and transient behaviour of laser processes enable control over phase transitions, heterostructure design, defect engineering, nucleation, compositional variations, recrystallization and amorphization, producing materials with interesting properties. Here we examine atomic- and nanoscale control in laser-assisted materials manufacturing. We discuss the laser processing synthesis and resultant properties of materials including metals, perovskites, graphene and other inorganic materials. The efficacy of atomic- and nanoscale modulation by laser processing is demonstrated by improved performance in diverse domains, including catalysis, mechanical reinforcement, electronics or optoelectronics, and drug screening. By emphasizing atomic-scale perspectives, this Review offers understanding of laser-assisted materials manufacturing while inspiring materials development. Laser technology offers high energy, precise spatial resolution and seamless automation for materials synthesis and device fabrication. This Review highlights laser-assisted materials engineering at the atomic and nanoscales and examines the laser-assisted discovery of materials with interesting properties and applications.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 12","pages":"1488-1503"},"PeriodicalIF":20.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680549","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 : 2025-12-03DOI: 10.1038/s44160-025-00946-w
Di Wang, Noah L. Mason, Fatemeh Karimi, Yinan Yang, Alexander S. Filatov, Young-Hwan Kim, Chenkun Zhou, De-en Jiang, Robert F. Klie, Dmitri V. Talapin
{"title":"Molecular organohalides as general precursors for direct synthesis of two-dimensional transition metal carbide MXenes","authors":"Di Wang, Noah L. Mason, Fatemeh Karimi, Yinan Yang, Alexander S. Filatov, Young-Hwan Kim, Chenkun Zhou, De-en Jiang, Robert F. Klie, Dmitri V. Talapin","doi":"10.1038/s44160-025-00946-w","DOIUrl":"https://doi.org/10.1038/s44160-025-00946-w","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665167","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 : 2025-12-01DOI: 10.1038/s44160-025-00952-y
Natalia M. Padial, Carlos Martí-Gastaldo
{"title":"Helically ordered polymers under metal–organic framework confinement","authors":"Natalia M. Padial, Carlos Martí-Gastaldo","doi":"10.1038/s44160-025-00952-y","DOIUrl":"https://doi.org/10.1038/s44160-025-00952-y","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645244","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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