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}
Pub Date : 2026-01-06DOI: 10.1038/s44160-025-00970-w
Dongqi Li, Wenhao Zheng, Mahdi Ghorbani-Asl, Juliane Scheiter, Kamil Sobczak, Silvan Kretschmer, Josef Polčák, Pranjali Hirasing Jadhao, Paweł P. Michałowski, Ruoling Yu, Jiaxu Zhang, Jinxin Liu, Jingwei Du, Quanquan Guo, Ehrenfried Zschech, Tomáš Šikola, Mischa Bonn, Nicolás Pérez, Kornelius Nielsch, Arkady V. Krasheninnikov, Hai I. Wang, Minghao Yu, Xinliang Feng
Surface terminations critically govern the properties of two-dimensional transition metal carbides and/or nitrides (MXenes), yet a universal strategy to obtain MXenes with uniform and controllable terminations remains elusive. Here we introduce a ‘gas–liquid–solid’ triphasic etching strategy that employs iodine vapour, halide molten salts and MAX phases to produce MXenes with pure and precisely tunable halogen terminations (Cl, Br, I or their combinations). In this process, halide molten salts dissolve iodine via interhalogen anion formation while efficiently transporting etching by-products. The resulting MXenes retain excellent structural integrity, yielding uniformly ordered surfaces. As a representative example, Ti 3 C 2 Cl 2 shows a 160-fold enhancement in macroscopic conductivity and a 13-fold enhancement in terahertz conductivity relative to conventional Cl/O-terminated Ti 3 C 2 , attributed to minimized electron trapping and scattering. Beyond single-halogen terminations, the gas–liquid–solid approach enables dual- and triple-halogen termination control, providing a general platform for tailoring MXene surface chemistry towards advanced (opto)electronic applications.
{"title":"Triphasic synthesis of MXenes with uniform and controlled halogen terminations","authors":"Dongqi Li, Wenhao Zheng, Mahdi Ghorbani-Asl, Juliane Scheiter, Kamil Sobczak, Silvan Kretschmer, Josef Polčák, Pranjali Hirasing Jadhao, Paweł P. Michałowski, Ruoling Yu, Jiaxu Zhang, Jinxin Liu, Jingwei Du, Quanquan Guo, Ehrenfried Zschech, Tomáš Šikola, Mischa Bonn, Nicolás Pérez, Kornelius Nielsch, Arkady V. Krasheninnikov, Hai I. Wang, Minghao Yu, Xinliang Feng","doi":"10.1038/s44160-025-00970-w","DOIUrl":"https://doi.org/10.1038/s44160-025-00970-w","url":null,"abstract":"Surface terminations critically govern the properties of two-dimensional transition metal carbides and/or nitrides (MXenes), yet a universal strategy to obtain MXenes with uniform and controllable terminations remains elusive. Here we introduce a ‘gas–liquid–solid’ triphasic etching strategy that employs iodine vapour, halide molten salts and MAX phases to produce MXenes with pure and precisely tunable halogen terminations (Cl, Br, I or their combinations). In this process, halide molten salts dissolve iodine via interhalogen anion formation while efficiently transporting etching by-products. The resulting MXenes retain excellent structural integrity, yielding uniformly ordered surfaces. As a representative example, Ti <jats:sub>3</jats:sub> C <jats:sub>2</jats:sub> Cl <jats:sub>2</jats:sub> shows a 160-fold enhancement in macroscopic conductivity and a 13-fold enhancement in terahertz conductivity relative to conventional Cl/O-terminated Ti <jats:sub>3</jats:sub> C <jats:sub>2</jats:sub> , attributed to minimized electron trapping and scattering. Beyond single-halogen terminations, the gas–liquid–solid approach enables dual- and triple-halogen termination control, providing a general platform for tailoring MXene surface chemistry towards advanced (opto)electronic applications.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903310","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 : 2026-01-05DOI: 10.1038/s44160-025-00951-z
Fuxing Shi, Nils Frank, Markus Leutzsch, Chendan Zhu, Nobuya Tsuji, Benjamin List
The precise manipulation of unfunctionalized hydrocarbons remains a fundamental challenge for chemical synthesis and catalysis. Stereodifferentiation in strained alkanes is particularly difficult to accomplish because a catalyst has to distinguish various highly exergonic chemo- and stereoselective strain-release channels. Here we disclose an organocatalytic asymmetric hydroalkoxylation of bicyclobutanes with alcohols to efficiently access tertiary cyclopropylcarbinyl ethers with high enantioselectivity (e.r. up to 98:2). Enantiocontrol is accomplished through chiral recognition between the confined iminoimidodiphosphoric acid catalyst and the substrate, mediated by non-covalent interactions between a Lewis basic binding site of the confined anion and the polarized C–H bond of the cyclopropylcarbinyl ion intermediate. Our work establishes bicyclobutane activation by harnessing strain-release energetics while maintaining precise stereo- and regiocontrol through structural confinement.
{"title":"Catalytic asymmetric activation of bicyclobutanes","authors":"Fuxing Shi, Nils Frank, Markus Leutzsch, Chendan Zhu, Nobuya Tsuji, Benjamin List","doi":"10.1038/s44160-025-00951-z","DOIUrl":"https://doi.org/10.1038/s44160-025-00951-z","url":null,"abstract":"The precise manipulation of unfunctionalized hydrocarbons remains a fundamental challenge for chemical synthesis and catalysis. Stereodifferentiation in strained alkanes is particularly difficult to accomplish because a catalyst has to distinguish various highly exergonic chemo- and stereoselective strain-release channels. Here we disclose an organocatalytic asymmetric hydroalkoxylation of bicyclobutanes with alcohols to efficiently access tertiary cyclopropylcarbinyl ethers with high enantioselectivity (e.r. up to 98:2). Enantiocontrol is accomplished through chiral recognition between the confined iminoimidodiphosphoric acid catalyst and the substrate, mediated by non-covalent interactions between a Lewis basic binding site of the confined anion and the polarized C–H bond of the cyclopropylcarbinyl ion intermediate. Our work establishes bicyclobutane activation by harnessing strain-release energetics while maintaining precise stereo- and regiocontrol through structural confinement.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"42 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903317","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 : 2026-01-05DOI: 10.1038/s44160-025-00984-4
Alexandra R. Groves
{"title":"Ammonia synthesis over AuRu alloys","authors":"Alexandra R. Groves","doi":"10.1038/s44160-025-00984-4","DOIUrl":"10.1038/s44160-025-00984-4","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"2-2"},"PeriodicalIF":20.0,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903312","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 : 2026-01-05DOI: 10.1038/s44160-025-00948-8
Nirmala Mohanta, Jacquelyne A. Read
Radical processes can be leveraged to impart meta selectivity in pyridine functionalization, offering a valuable approach for the late-stage functionalization of bioactive molecules.
自由基过程可以在吡啶功能化中赋予元选择性，为生物活性分子的后期功能化提供了有价值的方法。
{"title":"meta-Selective radical halogenation of pyridines","authors":"Nirmala Mohanta, Jacquelyne A. Read","doi":"10.1038/s44160-025-00948-8","DOIUrl":"10.1038/s44160-025-00948-8","url":null,"abstract":"Radical processes can be leveraged to impart meta selectivity in pyridine functionalization, offering a valuable approach for the late-stage functionalization of bioactive molecules.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"4-5"},"PeriodicalIF":20.0,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903314","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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