Pub Date : 2026-02-18DOI: 10.1038/s44160-026-00999-5
Yongchao Yang, Yuwei Yang, Jodie A. Yuwono, Soshan Cheong, Xinshuo Shi, Tingting Zhao, Richard D. Tilley, Nicholas M. Bedford, Shenlong Zhao
{"title":"High-entropy alloy nanowires for direct electrosynthesis of chlorine from seawater","authors":"Yongchao Yang, Yuwei Yang, Jodie A. Yuwono, Soshan Cheong, Xinshuo Shi, Tingting Zhao, Richard D. Tilley, Nicholas M. Bedford, Shenlong Zhao","doi":"10.1038/s44160-026-00999-5","DOIUrl":"https://doi.org/10.1038/s44160-026-00999-5","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146210449","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 : 2026-02-11DOI: 10.1038/s44160-026-00990-0
Ze-Xin Zhang, KaiChen Shu, Michael J. Tilby, Mark John P. Mandigma, Yiheng Guo, Jasper L. Tyler, Adam Noble, Varinder K. Aggarwal
Bioisosteric replacement of aromatic and heteroaromatic rings with bridged bicyclic hydrocarbons is an important strategy in drug discovery. Intramolecular [2+2] cycloadditions of unconjugated dienes can provide a route to such motifs but are governed by the ‘rule-of-five’, which dictates that five-membered rings are preferentially formed, limiting access to alternative ring sizes. Here we introduce a visible-light-mediated intramolecular [2 + 2] cycloaddition of aza-1,6-dienes that leverages radical stabilization strategies to enable the selective formation of bridged bicycles over typically favoured fused bicycles. This approach generates previously elusive 6-azabicyclo[3.1.1]heptanes with facile substitution at every position around the ring. Exit vector analysis and comparison of the physicochemical and pharmacological properties of a 6-azabicyclo[3.1.1]heptane analogue of a piperazine-based drug demonstrate the potential application of this scaffold in medicinal chemistry. The methodology enables access to new chemical space, with implications for drug discovery and beyond.
{"title":"Breaking the ‘rule-of-five’ to access bridged bicyclic heteroaromatic bioisosteres","authors":"Ze-Xin Zhang, KaiChen Shu, Michael J. Tilby, Mark John P. Mandigma, Yiheng Guo, Jasper L. Tyler, Adam Noble, Varinder K. Aggarwal","doi":"10.1038/s44160-026-00990-0","DOIUrl":"https://doi.org/10.1038/s44160-026-00990-0","url":null,"abstract":"Bioisosteric replacement of aromatic and heteroaromatic rings with bridged bicyclic hydrocarbons is an important strategy in drug discovery. Intramolecular [2+2] cycloadditions of unconjugated dienes can provide a route to such motifs but are governed by the ‘rule-of-five’, which dictates that five-membered rings are preferentially formed, limiting access to alternative ring sizes. Here we introduce a visible-light-mediated intramolecular [2 + 2] cycloaddition of aza-1,6-dienes that leverages radical stabilization strategies to enable the selective formation of bridged bicycles over typically favoured fused bicycles. This approach generates previously elusive 6-azabicyclo[3.1.1]heptanes with facile substitution at every position around the ring. Exit vector analysis and comparison of the physicochemical and pharmacological properties of a 6-azabicyclo[3.1.1]heptane analogue of a piperazine-based drug demonstrate the potential application of this scaffold in medicinal chemistry. The methodology enables access to new chemical space, with implications for drug discovery and beyond.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"34 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146152300","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 : 2026-02-02DOI: 10.1038/s44160-025-00964-8
Hau Sun Sam Chan, Yingzi Li, Jack L. Sutro, Daniel S. Brown, Robert S. Paton, Jonathan W. Burton
Despite numerous studies of trialkyloxonium ions in the literature, investigations into the chemistry of allylic, benzylic, propargylic and allenylic oxonium ions are rare. Existing reports on well-characterized allylic and benzylic oxonium ions invariably construct these species based on constrained tricyclic oxatriquinane or oxatriquinacene scaffolds, with only limited studies reported on unconstrained benzylic oxonium ions. Here we report an investigation on a collection of allylic, benzylic and hitherto unknown propargylic and allenylic oxonium ions prepared on unconstrained scaffolds by a general, modular and unified strategy. Permutation of the substitution pattern of these oxonium ions allowed the extension of the strategy for the syntheses of various doubly substituted oxonium ions. Most of these oxonium ions could be characterized at room temperature by NMR spectroscopy, and a series of unexpected reactions and chemical behaviours pertinent to these species are briefly described.
{"title":"Synthesis and properties of allylic, benzylic, propargylic and allenylic oxonium ions","authors":"Hau Sun Sam Chan, Yingzi Li, Jack L. Sutro, Daniel S. Brown, Robert S. Paton, Jonathan W. Burton","doi":"10.1038/s44160-025-00964-8","DOIUrl":"https://doi.org/10.1038/s44160-025-00964-8","url":null,"abstract":"Despite numerous studies of trialkyloxonium ions in the literature, investigations into the chemistry of allylic, benzylic, propargylic and allenylic oxonium ions are rare. Existing reports on well-characterized allylic and benzylic oxonium ions invariably construct these species based on constrained tricyclic oxatriquinane or oxatriquinacene scaffolds, with only limited studies reported on unconstrained benzylic oxonium ions. Here we report an investigation on a collection of allylic, benzylic and hitherto unknown propargylic and allenylic oxonium ions prepared on unconstrained scaffolds by a general, modular and unified strategy. Permutation of the substitution pattern of these oxonium ions allowed the extension of the strategy for the syntheses of various doubly substituted oxonium ions. Most of these oxonium ions could be characterized at room temperature by NMR spectroscopy, and a series of unexpected reactions and chemical behaviours pertinent to these species are briefly described.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"90 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102156","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 : 2026-02-02DOI: 10.1038/s44160-026-01002-x
Jet-Sing M. Lee
{"title":"Co-crystallizing stability into perovskite modules","authors":"Jet-Sing M. Lee","doi":"10.1038/s44160-026-01002-x","DOIUrl":"10.1038/s44160-026-01002-x","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"153-153"},"PeriodicalIF":20.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146155305","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 : 2026-02-02DOI: 10.1038/s44160-025-00987-1
Dong Gao, Long-Zhou Qin, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
The pervasive occurrence of chiral quaternary all-carbon stereocentres has stimulated great efforts towards the construction of such motifs. Among them, transition-metal-catalysed asymmetric radical C(sp3)–C(sp3) cross-coupling of racemic tertiary alkyl electrophiles with alkyl-based nucleophiles constitutes an appealing strategy, though it has rarely been reported. The major challenge lies in the sluggish interaction of transition-metal–alkyl species and sterically hindered tertiary alkyl radicals, which complicates both chemo- and enantiocontrol. Here we demonstrate a practical copper-catalysed enantioconvergent C(sp3)–C(sp3) cross-coupling of racemic tertiary electrophiles with easily accessed and bench-stable cyclopropanols under mild reaction conditions. Key to success is the rational design of quinine-derived N,N,N-ligands to form coordinatively saturated copper intermediates with low steric congestion around the metal centre to accommodate tertiary alkyl radicals. This protocol provides a highly flexible platform for the rapid synthesis of enantioenriched C(sp3)-rich building blocks with sterically crowded stereocentres that hold substantial interest in organic synthesis and related disciplines.
{"title":"Copper-catalysed enantioconvergent radical C(sp3)–C(sp3) cross-coupling of tertiary electrophiles with cyclopropanols for quaternary carbon formation","authors":"Dong Gao, Long-Zhou Qin, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu","doi":"10.1038/s44160-025-00987-1","DOIUrl":"https://doi.org/10.1038/s44160-025-00987-1","url":null,"abstract":"The pervasive occurrence of chiral quaternary all-carbon stereocentres has stimulated great efforts towards the construction of such motifs. Among them, transition-metal-catalysed asymmetric radical C(sp3)–C(sp3) cross-coupling of racemic tertiary alkyl electrophiles with alkyl-based nucleophiles constitutes an appealing strategy, though it has rarely been reported. The major challenge lies in the sluggish interaction of transition-metal–alkyl species and sterically hindered tertiary alkyl radicals, which complicates both chemo- and enantiocontrol. Here we demonstrate a practical copper-catalysed enantioconvergent C(sp3)–C(sp3) cross-coupling of racemic tertiary electrophiles with easily accessed and bench-stable cyclopropanols under mild reaction conditions. Key to success is the rational design of quinine-derived N,N,N-ligands to form coordinatively saturated copper intermediates with low steric congestion around the metal centre to accommodate tertiary alkyl radicals. This protocol provides a highly flexible platform for the rapid synthesis of enantioenriched C(sp3)-rich building blocks with sterically crowded stereocentres that hold substantial interest in organic synthesis and related disciplines.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102157","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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