In carbohydrate-based drug discovery, fluorine-containing substituents are widely used to enhance pharmacodynamic and pharmacokinetic profiles. However, the precise incorporation of C(sp3)-perfluoroalkyl moieties at the C2 position of sugar scaffolds remains a significant synthetic challenge. In this study, we report a highly efficient and cost-effective protocol for the synthesis of 2-deoxy-2-perfluoroalkyl glycosides from readily available glycals. This protocol demonstrates exceptional substrate generality, encompassing glucal, galactal, rhamnal, sialic acid, and arabinofuranose derivatives. More importantly, this platform enables the efficient synthesis of diverse C-, N-, and O-glycosides (over 50 examples) under gold(I)-catalyzed conditions, including the synthesis of previously inaccessible 2-deoxy-2-CF3-substituted nucleoside analogues. Additionally, photocatalytically generated 2-deoxy-2-CF3 glycosyl anomeric radicals readily undergo Giese-type additions to alkenes, affording alkylated glycosides, or engage in cross-coupling with aryl bromides to deliver antidiabetic drug candidates. Preliminary biological evaluations indicate that 2-deoxy-2-CF3-modified glycosides exhibit enhanced pharmacological properties, underscoring the translational potential of this synthetic technique for advancing carbohydrate-based therapeutics.
{"title":"Expeditious Synthesis of 2-Deoxy-2-perfluoroalkyl Glycosides","authors":"Shen Cao, Haobo Zhang, Niming Zhu, Peng Xu, Xiaoping Chen, Biao Yu, Xiaheng Zhang","doi":"10.1002/anie.1824435","DOIUrl":"https://doi.org/10.1002/anie.1824435","url":null,"abstract":"In carbohydrate-based drug discovery, fluorine-containing substituents are widely used to enhance pharmacodynamic and pharmacokinetic profiles. However, the precise incorporation of C(sp<sup>3</sup>)-perfluoroalkyl moieties at the C2 position of sugar scaffolds remains a significant synthetic challenge. In this study, we report a highly efficient and cost-effective protocol for the synthesis of 2-deoxy-2-perfluoroalkyl glycosides from readily available glycals. This protocol demonstrates exceptional substrate generality, encompassing glucal, galactal, rhamnal, sialic acid, and arabinofuranose derivatives. More importantly, this platform enables the efficient synthesis of diverse <i>C</i>-, <i>N</i>-, and <i>O</i>-glycosides (over 50 examples) under gold(I)-catalyzed conditions, including the synthesis of previously inaccessible 2-deoxy-2-CF<sub>3</sub>-substituted nucleoside analogues. Additionally, photocatalytically generated 2-deoxy-2-CF<sub>3</sub> glycosyl anomeric radicals readily undergo Giese-type additions to alkenes, affording alkylated glycosides, or engage in cross-coupling with aryl bromides to deliver antidiabetic drug candidates. Preliminary biological evaluations indicate that 2-deoxy-2-CF<sub>3</sub>-modified glycosides exhibit enhanced pharmacological properties, underscoring the translational potential of this synthetic technique for advancing carbohydrate-based therapeutics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139087","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}
Yongxin Yang, Kun Zeng, Yan Feng, Qi An, Lu Liu, Futong Ren, Xilin Liang, Genfu Zhao, Songsong Zhi, Hong Guo
The inherent factors influencing the growth of lithium (Li) dendrites and the kinetics of Li+ migration in polymer electrolytes lie in the electron cloud density distribution in the electrolyte. Localized electrons accumulation can trigger the uneven Li+ deposition, ultimately leading to battery failure. To address this critical challenge, the concept of p–π conjugation and B–O sp2 hybridization is innovatively incorporated into covalent organic frameworks (COFs) to mitigate local interfacial Li+ accumulation and improve Li+ migration kinetics in electrolytes by electron delocalization. Furthermore, perfluoroalkyl group with virtues of superior electron regulating capabilities and improved electrochemical-window, is strategically grafted to better match high-voltage cathodes. Under the synergistic role of electron regulation, the electrolyte with pπ–sp2-COF significantly improves overall electrochemical performance of solid-state batteries. Thus, regulating electron density via p-π conjugation and B-O sp2 hybridization promises to open new avenues for the development of COFs-modified polymer electrolytes in solid-state batteries.
{"title":"Modulating Electron Delocalization Structure in Covalent Organic Frameworks Through Conjugation and Hybridization to Boost Li-ion Migration Dynamics","authors":"Yongxin Yang, Kun Zeng, Yan Feng, Qi An, Lu Liu, Futong Ren, Xilin Liang, Genfu Zhao, Songsong Zhi, Hong Guo","doi":"10.1002/anie.202525864","DOIUrl":"https://doi.org/10.1002/anie.202525864","url":null,"abstract":"The inherent factors influencing the growth of lithium (Li) dendrites and the kinetics of Li<sup>+</sup> migration in polymer electrolytes lie in the electron cloud density distribution in the electrolyte. Localized electrons accumulation can trigger the uneven Li<sup>+</sup> deposition, ultimately leading to battery failure. To address this critical challenge, the concept of p–π conjugation and B–O sp<sup>2</sup> hybridization is innovatively incorporated into covalent organic frameworks (COFs) to mitigate local interfacial Li<sup>+</sup> accumulation and improve Li<sup>+</sup> migration kinetics in electrolytes by electron delocalization. Furthermore, perfluoroalkyl group with virtues of superior electron regulating capabilities and improved electrochemical-window, is strategically grafted to better match high-voltage cathodes. Under the synergistic role of electron regulation, the electrolyte with pπ–sp<sup>2</sup>-COF significantly improves overall electrochemical performance of solid-state batteries. Thus, regulating electron density via p-π conjugation and B-O sp<sup>2</sup> hybridization promises to open new avenues for the development of COFs-modified polymer electrolytes in solid-state batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139070","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}
Ikuya Fujii, Rin Seki, Haruka Kido, Louis Jauffret, Kazuhiko Semba, Yoshiaki Nakao
Here we describe the generation of aryl Grignard reagents from phenol derivatives via C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.
{"title":"Magnesiation of Phenol Derivatives Catalyzed by a Rhodium─Aluminum Complex","authors":"Ikuya Fujii, Rin Seki, Haruka Kido, Louis Jauffret, Kazuhiko Semba, Yoshiaki Nakao","doi":"10.1002/anie.202518631","DOIUrl":"https://doi.org/10.1002/anie.202518631","url":null,"abstract":"Here we describe the generation of aryl Grignard reagents from phenol derivatives <i>via</i> C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139067","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}
Dongxu Zhang, Deli Jiang, Yanhong Liu, Qitao Chen, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang, Baodong Mao
Modern electrocatalysis typically involves multi-species cascade systems, imposing stringent requirements on catalysts to exhibit multi-component and multifunctional characteristics. Such complexity poses great challenges for identifying and understanding the structural and functional nature of the true active phase. Herein, we report the formation of Cu111 nanolaminates confined within the interface of Cu1.94S/In2S3 heterojunction via in situ electrochemical reconstruction. The synthesized Cu111 nanolaminates act as a single-phase co-activating nanoreactor to preferentially adsorb carbon dioxide (CO2) and cascade N-intermediates, enabling C─N coupling for urea synthesis within an ultra-low and distinct potential window. The optimized Cu1.94S/Cu111/In2S3 catalyst achieves a urea yield rate of 11823.65 µg h−1 mgCu111−1 and an exceptionally high Faradaic efficiency of 69.34% at -0.35 V versus the reversible hydrogen electrode in a flow cell, surpassing all previously reported transition metal electrocatalysts. In situ spectroscopic analyses and theoretical calculations reveal a favorable reaction pathway and nanoconfined synergy on the Cu111 nanolaminates, where CO2 is initially anchored and reduced to *CO and cascaded *NO2 undergoes C─N coupling to form the key *CONO2 intermediate toward urea. This study unveils the true active phase within a complex heterostructure electrocatalyst, which also provides new insights into the rational design of advanced electrocatalysts for other energy and environmental applications.
{"title":"Confined Cu111 Nanolaminates as a Single-Phase Nanoreactor for Efficient Urea Electrosynthesis","authors":"Dongxu Zhang, Deli Jiang, Yanhong Liu, Qitao Chen, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang, Baodong Mao","doi":"10.1002/anie.2242110","DOIUrl":"https://doi.org/10.1002/anie.2242110","url":null,"abstract":"Modern electrocatalysis typically involves multi-species cascade systems, imposing stringent requirements on catalysts to exhibit multi-component and multifunctional characteristics. Such complexity poses great challenges for identifying and understanding the structural and functional nature of the true active phase. Herein, we report the formation of Cu<sub>111</sub> nanolaminates confined within the interface of Cu<sub>1.94</sub>S/In<sub>2</sub>S<sub>3</sub> heterojunction via in situ electrochemical reconstruction. The synthesized Cu<sub>111</sub> nanolaminates act as a single-phase co-activating nanoreactor to preferentially adsorb carbon dioxide (CO<sub>2</sub>) and cascade N-intermediates, enabling C─N coupling for urea synthesis within an ultra-low and distinct potential window. The optimized Cu<sub>1.94</sub>S/Cu<sub>111</sub>/In<sub>2</sub>S<sub>3</sub> catalyst achieves a urea yield rate of 11823.65 µg h<sup>−1</sup> mg<sub>Cu111</sub><sup>−1</sup> and an exceptionally high Faradaic efficiency of 69.34% at -0.35 V versus the reversible hydrogen electrode in a flow cell, surpassing all previously reported transition metal electrocatalysts. In situ spectroscopic analyses and theoretical calculations reveal a favorable reaction pathway and nanoconfined synergy on the Cu<sub>111</sub> nanolaminates, where CO<sub>2</sub> is initially anchored and reduced to *CO and cascaded *NO<sub>2</sub> undergoes C─N coupling to form the key *CONO<sub>2</sub> intermediate toward urea. This study unveils the true active phase within a complex heterostructure electrocatalyst, which also provides new insights into the rational design of advanced electrocatalysts for other energy and environmental applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139071","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}
Yulan Han, Jiayan Xu, Jiawei Wu, Chenyu Wu, Xiran Cheng, Wenbo Xie, Xiulian Pan, Xinhe Bao, P. Hu
Discovering next-generation heterogeneous catalysts calls for embracing the full complexity of active site formation under realistic conditions. Here, we develop a robust machine learning potential (MLP)-aided computational framework that integrates realistic preparation and reaction conditions to effectively track the formation of active sites and decipher structure-activity relationships. Using syngas conversion over the ZnxCryOz system as a demonstration, we identified that the system preferentially segregates into ZnO and ZnCr2O4 phases, with ZnO forming a monolayer on ZnCr2O4 surfaces under preparation conditions. Under reaction conditions, by deploying CH─O bond dissociation as a descriptor, we found that the ZnO/ZnCr2O4(100) surface is the active surface. Crucially, we pinpoint geometrically linked oxygen vacancy pairs as the true active sites. Full microkinetic analyses conducted on these active sites yield kinetic results that align well with experimental observations. Beyond elucidating the active structure, a model for designing oxide/oxide catalysts to achieve high activity is generalized, opening new pathways for accelerating catalyst discovery across a wide range of reactions.
{"title":"First Principles Identification of Active Sites in Heterogeneous Catalysis: A Case Study on ZnxCryOz for Syngas Conversion","authors":"Yulan Han, Jiayan Xu, Jiawei Wu, Chenyu Wu, Xiran Cheng, Wenbo Xie, Xiulian Pan, Xinhe Bao, P. Hu","doi":"10.1002/anie.202522416","DOIUrl":"https://doi.org/10.1002/anie.202522416","url":null,"abstract":"Discovering next-generation heterogeneous catalysts calls for embracing the full complexity of active site formation under realistic conditions. Here, we develop a robust machine learning potential (MLP)-aided computational framework that integrates realistic preparation and reaction conditions to effectively track the formation of active sites and decipher structure-activity relationships. Using syngas conversion over the Zn<sub>x</sub>Cr<sub>y</sub>O<sub>z</sub> system as a demonstration, we identified that the system preferentially segregates into ZnO and ZnCr<sub>2</sub>O<sub>4</sub> phases, with ZnO forming a monolayer on ZnCr<sub>2</sub>O<sub>4</sub> surfaces under preparation conditions. Under reaction conditions, by deploying CH─O bond dissociation as a descriptor, we found that the ZnO/ZnCr<sub>2</sub>O<sub>4</sub>(100) surface is the active surface. Crucially, we pinpoint geometrically linked oxygen vacancy pairs as the true active sites. Full microkinetic analyses conducted on these active sites yield kinetic results that align well with experimental observations. Beyond elucidating the active structure, a model for designing oxide/oxide catalysts to achieve high activity is generalized, opening new pathways for accelerating catalyst discovery across a wide range of reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139086","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}
Traditional heterogeneous photocatalytic systems coupled with oxidant activation hold great promise for environmental remediation but are constrained by radical scavenging and nonselective oxidation. Here, we introduce an overlooked photoswitch-mediated electron transfer (PSMET) mechanism that circumvents reactive oxygen species by enabling direct, ultrafast electron transfer from pollutants to oxidants through a photoactive mediator. Using environmentally benign bismuth oxyiodide as a model catalyst under visible-light irradiation, we achieve unprecedented degradation rates for various electron-rich pollutants such as sulfamethoxazole (t1/2 <2.0 min). This mechanism exhibits pollutant-dependent oxidant utilization mode and selective pollutant degradation characteristics. Mechanistic analyses reveal the formation of a high-potential electron-transfer pathway activated by photoexcitation, directly coupling pollutant oxidation to oxidant reduction within a single electron-transfer cycle. Frontier molecular orbital calculations further demonstrate that the narrow bandgap and p-type semiconductor characteristics selectively facilitate electron extraction from contaminants to oxidants. Remarkably, this PSMET mechanism displays universal applicability with diverse oxidants, maintaining >98% pollutant removals even in complex aqueous matrices and continuous-flow systems. Furthermore, the mechanism allows precise optical control over reaction initiation and termination, offering unparalleled spatiotemporal regulation for sustainable wastewater treatment. Our findings redefine photocatalytic oxidation paradigms and open new pathways toward energy-efficient, optically programmable, and environmentally sustainable remediation technologies.
{"title":"Photoswitch Mediated Electron Highway Driving Direct Pollutant-to-Oxidant Electron Transfer in Ultrafast Fenton-Like Reactions","authors":"Zhi-Quan Zhang, Bin-Bin Zhang, Jing Wang, Chang-Wei Bai, Xin-Jia Chen, Fu-Qiao Yang, Pi-Jun Duan, Fei Chen","doi":"10.1002/anie.202521687","DOIUrl":"https://doi.org/10.1002/anie.202521687","url":null,"abstract":"Traditional heterogeneous photocatalytic systems coupled with oxidant activation hold great promise for environmental remediation but are constrained by radical scavenging and nonselective oxidation. Here, we introduce an overlooked photoswitch-mediated electron transfer (PSMET) mechanism that circumvents reactive oxygen species by enabling direct, ultrafast electron transfer from pollutants to oxidants through a photoactive mediator. Using environmentally benign bismuth oxyiodide as a model catalyst under visible-light irradiation, we achieve unprecedented degradation rates for various electron-rich pollutants such as sulfamethoxazole (t<sub>1/2</sub> <2.0 min). This mechanism exhibits pollutant-dependent oxidant utilization mode and selective pollutant degradation characteristics. Mechanistic analyses reveal the formation of a high-potential electron-transfer pathway activated by photoexcitation, directly coupling pollutant oxidation to oxidant reduction within a single electron-transfer cycle. Frontier molecular orbital calculations further demonstrate that the narrow bandgap and p-type semiconductor characteristics selectively facilitate electron extraction from contaminants to oxidants. Remarkably, this PSMET mechanism displays universal applicability with diverse oxidants, maintaining >98% pollutant removals even in complex aqueous matrices and continuous-flow systems. Furthermore, the mechanism allows precise optical control over reaction initiation and termination, offering unparalleled spatiotemporal regulation for sustainable wastewater treatment. Our findings redefine photocatalytic oxidation paradigms and open new pathways toward energy-efficient, optically programmable, and environmentally sustainable remediation technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139068","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}
Izabela Kamińska, Justus T. Metternich, Alan M. Szalai, Carolin Smidoda, Sayantani Chakraborty, Lela Vukovic, Sebastian Kruss, Philip Tinnefeld
Single-walled carbon nanotubes (SWCNTs) are promising optical biosensing platforms due to their intrinsic near-infrared fluorescence and environmental sensitivity. While DNA-SWCNT hybrids have been widely studied, the structural arrangement of double-stranded DNA (dsDNA) on SWCNTs and its impact on exciton–fluorophore interactions remain insufficiently characterized. Here, we introduce carbon nanotube energy transfer with vertical nucleic acids (CNETvNA), in which fluorophores are positioned at defined distances from SWCNTs using guanine-defect anchored capture sequences hybridized with complementary oligonucleotides. By systematically varying the duplex length from 12 to 24 base pairs, we probe the distance dependence of dye–SWCNT interactions at the single-molecule level. Fluorescence lifetime imaging microscopy reveals efficient quenching of ATTO542 and ATTO643 dyes, with lifetime distributions reflecting heterogeneous duplex conformations. Molecular dynamics simulations demonstrate that dsDNA duplexes adopt a predominantly perpendicular orientation relative to the SWCNT axis, with increasing tilt and conformational variability at longer lengths. Combining experimental and computational results, we establish a distance dependence of d−5 with 7.4 ± 0.7 nm for 50% quenching efficiency, consistent with theoretical predictions for point dipole donors and 1D acceptors. These findings provide structural insights into DNA-SWCNT conjugates and establish CNETvNA as a rational design principle for SWCNT-based biosensors.
{"title":"Distance-Dependent Energy Transfer Between Organic Fluorophores and Single-Walled Carbon Nanotubes","authors":"Izabela Kamińska, Justus T. Metternich, Alan M. Szalai, Carolin Smidoda, Sayantani Chakraborty, Lela Vukovic, Sebastian Kruss, Philip Tinnefeld","doi":"10.1002/anie.202520411","DOIUrl":"https://doi.org/10.1002/anie.202520411","url":null,"abstract":"Single-walled carbon nanotubes (SWCNTs) are promising optical biosensing platforms due to their intrinsic near-infrared fluorescence and environmental sensitivity. While DNA-SWCNT hybrids have been widely studied, the structural arrangement of double-stranded DNA (dsDNA) on SWCNTs and its impact on exciton–fluorophore interactions remain insufficiently characterized. Here, we introduce carbon nanotube energy transfer with vertical nucleic acids (CNETvNA), in which fluorophores are positioned at defined distances from SWCNTs using guanine-defect anchored capture sequences hybridized with complementary oligonucleotides. By systematically varying the duplex length from 12 to 24 base pairs, we probe the distance dependence of dye–SWCNT interactions at the single-molecule level. Fluorescence lifetime imaging microscopy reveals efficient quenching of ATTO542 and ATTO643 dyes, with lifetime distributions reflecting heterogeneous duplex conformations. Molecular dynamics simulations demonstrate that dsDNA duplexes adopt a predominantly perpendicular orientation relative to the SWCNT axis, with increasing tilt and conformational variability at longer lengths. Combining experimental and computational results, we establish a distance dependence of d<sup>−</sup><sup>5</sup> with 7.4 ± 0.7 nm for 50% quenching efficiency, consistent with theoretical predictions for point dipole donors and 1D acceptors. These findings provide structural insights into DNA-SWCNT conjugates and establish CNETvNA as a rational design principle for SWCNT-based biosensors.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"241 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139069","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}
Nucleic acids are essential biological macromolecules bearing genetic information and playing important roles in post-transcriptional regulation. Given their high programmability based on Watson–Crick–Franklin base-pairing interactions, synthetic DNA and RNA oligonucleotides have become versatile building blocks for programmable assembly of nanostructures, nanomachines, and macroscopic materials. Recent discoveries have shown that long-chain nucleic acids can undergo temperature-induced phase separation, enabling rapid and facile formation of micro-sized, nucleic acid-rich condensates. Unlike conventional DNA/RNA nanotechnology, which relies primarily on base-pairing interactions, phase separation leverages the intrinsic polymeric nature of nucleic acids. While it expands the scope of DNA/RNA nanotechnology for new applications, nucleic acid phase separation also provides a fresh perspective for how compartmentalization may have emerged in the prebiotic RNA world during the origin of life. In this Minireview, we discuss the current mechanistic understanding of temperature-induced phase separation of synthetic long-chain DNA and RNA in vitro, in the absence of complex coacervation with proteins and polymers. We highlight strategies for controlling the physical and chemical properties of DNA condensates and review the progress and advances in developing them for various applications.
{"title":"Phase Separation of Nucleic Acids: Mechanisms, Properties, and Applications","authors":"Weixiang Chen, Johann Fritzen, Andreas Walther","doi":"10.1002/anie.202523943","DOIUrl":"https://doi.org/10.1002/anie.202523943","url":null,"abstract":"Nucleic acids are essential biological macromolecules bearing genetic information and playing important roles in post-transcriptional regulation. Given their high programmability based on Watson–Crick–Franklin base-pairing interactions, synthetic DNA and RNA oligonucleotides have become versatile building blocks for programmable assembly of nanostructures, nanomachines, and macroscopic materials. Recent discoveries have shown that long-chain nucleic acids can undergo temperature-induced phase separation, enabling rapid and facile formation of micro-sized, nucleic acid-rich condensates. Unlike conventional DNA/RNA nanotechnology, which relies primarily on base-pairing interactions, phase separation leverages the intrinsic polymeric nature of nucleic acids. While it expands the scope of DNA/RNA nanotechnology for new applications, nucleic acid phase separation also provides a fresh perspective for how compartmentalization may have emerged in the prebiotic RNA world during the origin of life. In this Minireview, we discuss the current mechanistic understanding of temperature-induced phase separation of synthetic long-chain DNA and RNA in vitro, in the absence of complex coacervation with proteins and polymers. We highlight strategies for controlling the physical and chemical properties of DNA condensates and review the progress and advances in developing them for various applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116132","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}
Feng Gao, Hai Wu, Jingwei Zhang, Peng Wang, Jun Deng
We report the first total syntheses of curtachalasin B and a series of biosynthetically related cytochalasans, including ketocytochalasin, xylariasins, brunnesins, zygosporins, arbuschalasins, cytochalasins, and curtachalasin Q, derived from the common precursor zygosporin G. The key intermediate was strategically assembled through an intermolecular Diels–Alder reaction, two Horner–Wadsworth–Emmons (HWE) macrocyclizations, and a late-stage methyl 1,2-addition. The highly functionalized 6/6 ring system of curtachalasin B was efficiently constructed through a biosynthetic network analysis inspired transannular cyclization and α-ketol rearrangement cascade. This unified skeletal reorganization strategy not only accomplished the first total synthesis of fifteen cytochalasans but also provided compelling experimental support for the proposed biosynthetic pathway of curtachalasin B, thereby establishing a chemical link between multiple subclasses of this family.
我们报道了首次合成curtachalasin B和一系列生物合成相关的细胞松弛素，包括酮细胞松弛素、木木松弛素、brunnesins、zygosporins、丛枝松弛素、细胞松弛素和curtachalasin Q，这些细胞松弛素是由共同的前体zygosporin g衍生而来的。关键中间体通过分子间diols - alder反应、两次Horner-Wadsworth-Emmons （HWE）大环化和后期甲基1,2-加成进行了有策略的组装。通过跨环环化和α-酮重排级联的生物合成网络分析，高效构建了高功能化的curtachalasin B 6/6环体系。这种统一的骨骼重组策略不仅首次完成了15种细胞chalasans的全合成，而且为提出的curtachalasin B的生物合成途径提供了强有力的实验支持，从而在该家族的多个亚类之间建立了化学联系。
{"title":"Bioinspired Total Synthesis of Curtachalasin B and Biosynthetically Related Cytochalasans","authors":"Feng Gao, Hai Wu, Jingwei Zhang, Peng Wang, Jun Deng","doi":"10.1002/anie.202524740","DOIUrl":"https://doi.org/10.1002/anie.202524740","url":null,"abstract":"We report the first total syntheses of curtachalasin B and a series of biosynthetically related cytochalasans, including ketocytochalasin, xylariasins, brunnesins, zygosporins, arbuschalasins, cytochalasins, and curtachalasin Q, derived from the common precursor zygosporin G. The key intermediate was strategically assembled through an intermolecular Diels–Alder reaction, two Horner–Wadsworth–Emmons (HWE) macrocyclizations, and a late-stage methyl 1,2-addition. The highly functionalized 6/6 ring system of curtachalasin B was efficiently constructed through a biosynthetic network analysis inspired transannular cyclization and α-ketol rearrangement cascade. This unified skeletal reorganization strategy not only accomplished the first total synthesis of fifteen cytochalasans but also provided compelling experimental support for the proposed biosynthetic pathway of curtachalasin B, thereby establishing a chemical link between multiple subclasses of this family.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"223 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102052","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}
In traditional transition-metal-catalyzed cross-coupling reactions, alkenyl electrophiles typically undergo transformation at the ipso-position of the leaving group, resulting in the formation of a single bond, rather than the installation of two functionalities across a C═C unit. Achieving the direct difunctionalization of alkenyl electrophiles has become increasingly desirable for streamlining the synthesis of complex molecules, which is essential for advancing molecular complexity in organic synthesis. Here, we report an iron-catalyzed cine-reductive carboboration of alkenyl tosylates with alkyl halides, providing a streamlined route to synthetically valuable tetrasubstituted alkenyl boronates. Mechanistic studies support a pathway that involves selective cine-alkylation of alkenyl tosylates followed by borylation, enabling the sequential formation of C(sp3)─C(sp3) and C(sp3)─B bonds, with subsequent elimination affording the desired C(sp2)─C(sp2) and C(sp2)─B bonds. These findings not only provide new mechanistic insights into iron-catalyzed cine-coupling processes but also establish a foundation for the rational design of new transformations of alkenyl electrophiles under iron catalysis.
{"title":"Cine-Reductive Carboboration of Alkenyl Electrophiles via Iron Catalysis","authors":"Adong Qiao, Shasha Geng, Xianrong Chen, Jinping Yuan, Yun He, Mei Bai, Zhang Feng","doi":"10.1002/anie.202525623","DOIUrl":"https://doi.org/10.1002/anie.202525623","url":null,"abstract":"In traditional transition-metal-catalyzed cross-coupling reactions, alkenyl electrophiles typically undergo transformation at the <i>ipso</i>-position of the leaving group, resulting in the formation of a single bond, rather than the installation of two functionalities across a C═C unit. Achieving the direct difunctionalization of alkenyl electrophiles has become increasingly desirable for streamlining the synthesis of complex molecules, which is essential for advancing molecular complexity in organic synthesis. Here, we report an iron-catalyzed <i>cine</i>-reductive carboboration of alkenyl tosylates with alkyl halides, providing a streamlined route to synthetically valuable tetrasubstituted alkenyl boronates. Mechanistic studies support a pathway that involves selective <i>cine</i>-alkylation of alkenyl tosylates followed by borylation, enabling the sequential formation of C(sp<sup>3</sup>)─C(sp<sup>3</sup>) and C(sp<sup>3</sup>)─B bonds, with subsequent elimination affording the desired C(sp<sup>2</sup>)─C(sp<sup>2</sup>) and C(sp<sup>2</sup>)─B bonds. These findings not only provide new mechanistic insights into iron-catalyzed <i>cine</i>-coupling processes but also establish a foundation for the rational design of new transformations of alkenyl electrophiles under iron catalysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101955","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}
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