Nature chemistry最新文献_第2页

Core diversification using 1,2-oxaborines as a versatile molecular platform. 核心多样化使用1,2-二氧aborines作为多功能分子平台。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-09 DOI: 10.1038/s41557-025-01971-0

Yao Ge, Qi Zhu, Yongqi Zhu, Guangbin Dong

引用次数: 0

Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer. 热化学杂解加氢催化通过极化驱动氢化物转移进行。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-09 DOI: 10.1038/s41557-025-01939-0

Hai-Xu Wang, Yogesh Surendranath

{"title":"Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer.","authors":"Hai-Xu Wang, Yogesh Surendranath","doi":"10.1038/s41557-025-01939-0","DOIUrl":"https://doi.org/10.1038/s41557-025-01939-0","url":null,"abstract":"Heterolytic hydrogenations, which split H2 across a hydride acceptor and proton acceptor, comprise a key reaction class that spans the chemical value chain, including CO2 hydrogenation to formate and NADH regeneration from nicotinamide adenine dinucleotide (NAD+). The dominant mechanistic models for heterogeneous catalysis of these reactions invoke classical surface reaction steps, largely ignoring the role of interfacial charge separation. Here we quantify the electrochemical potential of the catalyst during turnover and uncover evidence supporting an interfacial electrochemical hydride transfer mechanism for this overall thermochemical reaction class. We find that the proton acceptor induces spontaneous electrochemical polarization of the metal catalyst surface, thereby controlling the thermodynamic hydricity of the surface M-H intermediates and driving rate-determining electrochemical hydride transfer to the hydride acceptor substrate. This mechanistic framework, which applies across diverse reaction media and for the hydrogenation of CO2 to formate and NAD+ to NADH, enables the determination of intrinsic reaction kinetics and exposes design principles for the future development of sustainable hydrogenation reactivity.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145258551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cross-electrophile coupling of polyfluoroarenes and aryl chlorides. 多氟芳烃与芳酰氯的亲电偶联。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-08 DOI: 10.1038/s41557-025-01961-2

引用次数: 0

Covalent organic frameworks as infinite building units for metal-organic frameworks with compartmentalized pores. 共价有机框架作为具有分隔孔的金属有机框架的无限构建单元。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-07 DOI: 10.1038/s41557-025-01953-2

Bo Liu, Yichen Wu, Linxia Wang, Hai-Long Jiang, Qiaowei Li

{"title":"Covalent organic frameworks as infinite building units for metal-organic frameworks with compartmentalized pores.","authors":"Bo Liu, Yichen Wu, Linxia Wang, Hai-Long Jiang, Qiaowei Li","doi":"10.1038/s41557-025-01953-2","DOIUrl":"https://doi.org/10.1038/s41557-025-01953-2","url":null,"abstract":"Metal-organic frameworks typically rely on discrete molecules as building units, and creating frameworks featuring continuous organic or inorganic subnet moieties, such as chains and layers, is challenging. While all-inorganic subnets have been used as units with infinite connectivity, the intrinsic disorder in organic chains and layers hinders their role as well-defined building blocks for reticular materials. Here we report the one-pot synthesis of a series of Zr6O8-based or Hf6O8-based metal-organic frameworks that feature boroxine-based one-dimensional and two-dimensional covalent organic frameworks-chains with diverse conformations and layers with specific topology, respectively-as the organic components. The spatial compatibility between the constituents locks the infinite organic units into patterned arrangements and thus generates metal-organic frameworks with distinct structural entities and pore environments in separate sections along specific directions. The coexistence of extended covalent organic frameworks and discrete inorganic units, side by side and yet independent of each other, leads to high structural compartmentalization in space.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145244757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Triplet state reactivity of iminium ions in organocatalytic asymmetric [2 + 2] photocycloadditions. 有机催化不对称[2 + 2]光环加成中微量离子的三重态反应性。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-06 DOI: 10.1038/s41557-025-01960-3

Vasco Corti, Gianluca Simionato, Lorenzo Rizzo, Stefano A Serapian, Giorgio Pelosi, Mirco Natali, Luca Dell'Amico

{"title":"Triplet state reactivity of iminium ions in organocatalytic asymmetric [2 + 2] photocycloadditions.","authors":"Vasco Corti, Gianluca Simionato, Lorenzo Rizzo, Stefano A Serapian, Giorgio Pelosi, Mirco Natali, Luca Dell'Amico","doi":"10.1038/s41557-025-01960-3","DOIUrl":"https://doi.org/10.1038/s41557-025-01960-3","url":null,"abstract":"Organic transformations mediated by the transient formation of iminium ions have shown remarkable synthetic potential for the construction of enantioenriched molecules. The possibility to access their first singlet excited state (S1) under light irradiation has led to the development of previously inaccessible transformations. However, the triplet state (T1) reactivity remains limited and typically requires external photosensitizers. Here we show that structurally modified chiral iminium ions, integrated into extended π-systems, directly engage in T1 reactivity. This modified conjugated architecture was designed to overcome the intrinsic photophysical limitations of conventional iminium ion chemistry, enabling access to previously inaccessible excited-state reaction manifolds. The resulting system allows organocatalytic enantioselective [2 + 2] photocycloadditions without the need for external sensitizers. Mechanistic studies, involving spectroscopic techniques and computational methods, elucidate the role of the T1 intermediate as the key reactive intermediate.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145239235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unlocking red-to-near-infrared luminescence via ion-pair assembly in carbodicarbene borenium ions. 通过碳二苯硼离子离子对组装解锁红至近红外发光。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-06 DOI: 10.1038/s41557-025-01941-6

Chun-Lin Deng, Bi Youan E Tra, Xibao Zhang, Chonghe Zhang, Robert J Gilliard

{"title":"Unlocking red-to-near-infrared luminescence via ion-pair assembly in carbodicarbene borenium ions.","authors":"Chun-Lin Deng, Bi Youan E Tra, Xibao Zhang, Chonghe Zhang, Robert J Gilliard","doi":"10.1038/s41557-025-01941-6","DOIUrl":"https://doi.org/10.1038/s41557-025-01941-6","url":null,"abstract":"Achieving efficient red and near-infrared (NIR) emission in boron cation-based emitters remains challenging owing to their intrinsic instability, strong electrophilicity of the boron centre and pronounced non-radiative decay governed by the energy gap law. Here we report a family of air- and moisture-stable carbodicarbene (CDC)-borabenzo[c]anthanthrenium ions exhibiting solid-state red-to-NIR luminescence (maximum emission wavelength up to 730 nm) with competitive quantum yields. Crystallographic, photophysical and computational analyses reveal that the CDC ligand plays a dual role by electronically stabilizing the boron centre and directing ion-pair assembly via charge localization, thereby modulating exciton coupling and aggregate-state emission. These cationic π-extended boron frameworks represent rare examples of monoboron-doped luminophores displaying deep-red-to-NIR emission. Our findings highlight that the combination of π-extension, a charge-directing CDC ligand and ion-pair assembly constitutes an effective strategy to access efficient red/NIR emitters, providing guiding principles for the design of functional long-wavelength emitting main-group materials.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145239301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enantioconvergent radical addition of racemic alkyl halides to access vicinal stereocentres. 外消旋烷基卤化物的对映收敛自由基加成以接近相邻的立体中心。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-06 DOI: 10.1038/s41557-025-01967-w

Xianqing Wu, Tingting Xia, Jiahao Bai, Yue Shi, Chengxu Fang, Jiangtao Hu, Wenwen Wu, Chenhuan Zhang, Qinglin Wang, Genping Huang, Jingping Qu, Yifeng Chen

{"title":"Enantioconvergent radical addition of racemic alkyl halides to access vicinal stereocentres.","authors":"Xianqing Wu, Tingting Xia, Jiahao Bai, Yue Shi, Chengxu Fang, Jiangtao Hu, Wenwen Wu, Chenhuan Zhang, Qinglin Wang, Genping Huang, Jingping Qu, Yifeng Chen","doi":"10.1038/s41557-025-01967-w","DOIUrl":"https://doi.org/10.1038/s41557-025-01967-w","url":null,"abstract":"The development of synthetic methods that convert readily accessible chemicals into highly valuable small organic molecules, especially those with enantioenriched three-dimensional structures, holds substantial importance in organic synthesis. Alkyl halides are pivotal substrates for generating chiral C(sp3)-C(sp3) bonds. However, constructing modular vicinal stereogenic carbon centres from racemic alkyl halides, especially those bearing the sterically bulky quaternary carbon stereocentres frequently found in natural products, remains a daunting challenge. Here we report cobalt-catalysed enantioconvergent reductive addition of racemic alkyl halides with imines, allowing for efficient construction of various contiguous stereogenic centres, including tertiary-tertiary, tertiary-quaternary and quaternary-quaternary stereocentres with high diastereo- and enantioselectivities. The mild reaction conditions circumvent the use of organometallic reagents, ensuring broad functional group compatibility and enabling the formation of valuable chiral organic motifs such as amino acids, organophosphorus compounds, amino alcohols and γ-lactams. This reductive radical addition protocol also enables the stereoselective construction of C-glycosyl amino acids.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145239303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Selective arylation of atypical C-F bonds in polyfluoroarenes with aryl chlorides. 非典型C-F键与芳酰氯的选择性芳基化。

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-10-03 DOI: 10.1038/s41557-025-01962-1

Zhi Liu,Chaoyu Du,Jie Han,Xiaoliang Yang,Siyu Xia,Kai Liu,Chengjian Zhu,Weipeng Li,Jin Xie

{"title":"Selective arylation of atypical C-F bonds in polyfluoroarenes with aryl chlorides.","authors":"Zhi Liu,Chaoyu Du,Jie Han,Xiaoliang Yang,Siyu Xia,Kai Liu,Chengjian Zhu,Weipeng Li,Jin Xie","doi":"10.1038/s41557-025-01962-1","DOIUrl":"https://doi.org/10.1038/s41557-025-01962-1","url":null,"abstract":"Selective activation of specific C-F bonds in polyfluoroarenes represents a challenge in transition metal catalysis. Here we report a photoexcited nickel-catalysed cross-electrophile coupling between polyfluoroarenes and aryl chlorides, achieving highly selective arylation at atypical C-F sites of fluoroarenes, facilitated by a synergistic lithium salt effect. A wide range of structurally diverse fluorine-containing biaryls are obtained in 33-94% yields with satisfying C-F regioselectivity. Notably, the observed regioselectivity is atypical and complements existing methodologies, such as palladium-catalysed and visible-light photoredox-catalysed defluorinative functionalization reactions. Our mechanistic studies and theoretical calculations suggest that the lithium salt could interact with both pentafluorobenzene and the Ni catalyst, effectively lowering the energy barrier and modulating the regioselectivity. The synthetic versatility of our approach is underscored by late-stage synthetic application and sequential functionalization of multiple C-F bonds, which further demonstrates its robust utility in concisely constructing partially fluorinated and biologically interesting compounds.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"121 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216008","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Divergent access to E- or Z-trisubstituted medium-sized cycloalkenes by Pd-catalysed cycloaddition. 钯催化环加成对E-或z -三取代中型环烯烃的歧化反应。

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-10-03 DOI: 10.1038/s41557-025-01933-6

Gong-Feng Zou,Wenxuan Lin,Lin Shi,Bin-Miao Yang,Yu Lan,Yu Zhao

{"title":"Divergent access to E- or Z-trisubstituted medium-sized cycloalkenes by Pd-catalysed cycloaddition.","authors":"Gong-Feng Zou,Wenxuan Lin,Lin Shi,Bin-Miao Yang,Yu Lan,Yu Zhao","doi":"10.1038/s41557-025-01933-6","DOIUrl":"https://doi.org/10.1038/s41557-025-01933-6","url":null,"abstract":"Despite their significance in nature, medium-sized rings (particularly 9-11 membered ones) are non-existent in commercial small-molecule drugs largely due to the lack of efficient syntheses. Even with the widespread presence of macrocyclic alkenes in therapeutic agents, stereoselective access to either E- or Z-alkenes remains a formidable challenge. The few available methods for stereoselective macrocyclic alkene synthesis necessitate the use of geometrically pure E- or Z-alkene starting materials. Here we report the construction of 11-membered heterocyclic alkenes through Pd-catalysed formal cycloaddition of two readily available building blocks. This catalytic method also achieves a ligand-induced catalytic divergent preparation of either E- or Z-trisubstituted cycloalkenes starting from common terminal alkene substrates. Density functional theory calculations establish that the key alkoxide-chelated Pd-π-allyl intermediate adopts η1 or η3 coordination depending on the ligand used. This leads to allylic substitution using opposite π-allyl faces and in turn E- or Z-geometry in the cycloalkene products.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"86 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Leveraging electron donor-acceptor complexes for kinetic resolution in catalytic asymmetric photochemical synthesis. 利用电子给体-受体配合物在催化不对称光化学合成中的动力学分辨。

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-10-03 DOI: 10.1038/s41557-025-01973-y

Tianju Shao, Zongxun Li, Feiyun Nie, Qiang Li, Xiaowei Zhao, Zhiyong Jiang

{"title":"Leveraging electron donor-acceptor complexes for kinetic resolution in catalytic asymmetric photochemical synthesis.","authors":"Tianju Shao, Zongxun Li, Feiyun Nie, Qiang Li, Xiaowei Zhao, Zhiyong Jiang","doi":"10.1038/s41557-025-01973-y","DOIUrl":"10.1038/s41557-025-01973-y","url":null,"abstract":"The formation of electron donor-acceptor (EDA) complexes has emerged as a powerful strategy for accessing valuable molecules. However, protocols for constructing enantio-enriched molecules are limited, typically relying on EDA complex formation between a substrate and an intermediate generated from a chiral catalyst along with another substrate. This approach facilitates the coupling of the resulting radical species, thereby enabling the controlled enantioselective formation of stereocentres. Here we introduce a kinetic resolution strategy that harnesses the formation of EDA complexes between a chiral catalyst and racemic feedstock. The key lies in the thermodynamic disparity of the chiral catalyst's interaction with the two enantiomers of the substrate, which is critical for enabling subsequent transformations under a kinetic control. We demonstrate that photochemical reactions involving racemic azaarene-functionalized tertiary alcohols and amines, together with a chiral phosphoric acid, yield enantio-enriched derivatives containing tertiary carbon stereocentres. The utility of this approach is further exemplified by synthesizing important azaarene variants featuring tertiary or secondary C-F bonds, as well as ethylene oxides.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145225632","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0