Bo Li, Xingyi He, Yizhi Zhang, Kang Li, Yingmo Zhang, Shanshan Liu, Yu‐Cheng Gu, Xiao Shen
Organosilicon reagents play a significant role in the preparation of molecules essential to synthetic chemistry, materials science, and medicinal chemistry. However, selectively transforming strong C( sp 3 )─Si bonds in unactivated organosilicon reagents remains a significant challenge due to their high stability and low reactivity. Herein, we report that hydroxyl radical generated from water (H 2 O) can effectively drive the homolysis of strong C( sp 3 )─Si bonds, enabling radical alkylation with electron‐deficient alkenes. We reveal that H 2 O facilitates the generation of alkyl radicals, including tertiary, secondary, and primary radicals. Even the inert Et 4 Si can be activated and used in radical alkylation under our methodology. Moreover, we show that this strategy can be applied to the radical difunctionalization of silacycles, leading to the synthesis of organosilicon compounds not previously achievable through other methods. We anticipate that this approach will serve as a foundation for the development of more advanced radical reactions with unactivated organosilicon reagents, thereby facilitating the synthesis of a wide range of valuable molecules.
{"title":"Hydroxyl Radicals Unlock Strong C( sp 3 )─Si Bonds: Photocatalytic Alkylation and Silacycle Engineering","authors":"Bo Li, Xingyi He, Yizhi Zhang, Kang Li, Yingmo Zhang, Shanshan Liu, Yu‐Cheng Gu, Xiao Shen","doi":"10.1002/anie.202523587","DOIUrl":"https://doi.org/10.1002/anie.202523587","url":null,"abstract":"Organosilicon reagents play a significant role in the preparation of molecules essential to synthetic chemistry, materials science, and medicinal chemistry. However, selectively transforming strong C( <jats:italic> sp <jats:sup>3</jats:sup> </jats:italic> )─Si bonds in unactivated organosilicon reagents remains a significant challenge due to their high stability and low reactivity. Herein, we report that hydroxyl radical generated from water (H <jats:sub>2</jats:sub> O) can effectively drive the homolysis of strong C( <jats:italic> sp <jats:sup>3</jats:sup> </jats:italic> )─Si bonds, enabling radical alkylation with electron‐deficient alkenes. We reveal that H <jats:sub>2</jats:sub> O facilitates the generation of alkyl radicals, including tertiary, secondary, and primary radicals. Even the inert Et <jats:sub>4</jats:sub> Si can be activated and used in radical alkylation under our methodology. Moreover, we show that this strategy can be applied to the radical difunctionalization of silacycles, leading to the synthesis of organosilicon compounds not previously achievable through other methods. We anticipate that this approach will serve as a foundation for the development of more advanced radical reactions with unactivated organosilicon reagents, thereby facilitating the synthesis of a wide range of valuable molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732043","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}
Photocatalytic hydrogen evolution efficiency is critically dependent on electron transfer between photosensitizers (PSs) and catalysts. Herein, covalent assembly of Ir‐PSs with Co 7 polyoxometalate was achieved via Schiff‐base condensation to adjust electron transfer pathways, the resulting Ir‐2@Co 7 assembly exhibits a turnover number of 2280 for H 2 evolution, ∼18 and ∼253 times higher than that of its physically mixture and Ir‐1@Co 7 , respectively. Moreover, the generated H 2 can drive tandem styrene hydrogenation under ambient conditions, achieving 99.9% ethylbenzene yield. Spectroscopic and thermodynamic analyses reveal that covalent linkage switches dominant quenching mechanism from reductive to oxidative, and dramatically enhances electron quenching rate constant by over two orders of magnitude from 2.54 × 10 9 M −1 s −1 in physical‐mixed system to 5.87 × 10 11 M −1 s −1 in the assembly. This work highlights the key role of covalent integration in promoting electron transfer, providing a general design principle for developing high‐performance H 2 evolution and tandem hydrogenation systems.
{"title":"Modulating Electron‐Transfer via Covalent Assembly Polyoxometalate with Photosensitizer for Efficient H 2 Evolution and Tandem Hydrogenation","authors":"Shen‐Yue Xu, Ping Wang, Song Guo, Shuang Yao, Cheng Wang, Tong‐Bu Lu, Zhi‐Ming Zhang","doi":"10.1002/anie.202523472","DOIUrl":"https://doi.org/10.1002/anie.202523472","url":null,"abstract":"Photocatalytic hydrogen evolution efficiency is critically dependent on electron transfer between photosensitizers (PSs) and catalysts. Herein, covalent assembly of Ir‐PSs with Co <jats:sub>7</jats:sub> polyoxometalate was achieved via Schiff‐base condensation to adjust electron transfer pathways, the resulting Ir‐2@Co <jats:sub>7</jats:sub> assembly exhibits a turnover number of 2280 for H <jats:sub>2</jats:sub> evolution, ∼18 and ∼253 times higher than that of its physically mixture and Ir‐1@Co <jats:sub>7</jats:sub> , respectively. Moreover, the generated H <jats:sub>2</jats:sub> can drive tandem styrene hydrogenation under ambient conditions, achieving 99.9% ethylbenzene yield. Spectroscopic and thermodynamic analyses reveal that covalent linkage switches dominant quenching mechanism from reductive to oxidative, and dramatically enhances electron quenching rate constant by over two orders of magnitude from 2.54 × 10 <jats:sup>9</jats:sup> M <jats:sup>−1</jats:sup> s <jats:sup>−1</jats:sup> in physical‐mixed system to 5.87 × 10 <jats:sup>11</jats:sup> M <jats:sup>−1</jats:sup> s <jats:sup>−1</jats:sup> in the assembly. This work highlights the key role of covalent integration in promoting electron transfer, providing a general design principle for developing high‐performance H <jats:sub>2</jats:sub> evolution and tandem hydrogenation systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731808","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}
The stabilization and multifunctionalization of radicals constitute two major challenges. We introduce a “kill two birds with one stone” methodology and illustrate the production of Au 64 (CPT) 31 S· from the newly obtained precursor nanocluster Au 64 (CPT) 32 (CPT: cyclopentanethiolate). Despite the isolated Au 64 (CPT) 31 S· are ultrastable (maintain the majority under 100 °C for 2 h in an atmospheric solution environment), they can initiate the polymerization of pentaerythritol triacrylate in 3D printing. In addition, the superradicial(which means it is not a single (super)atom but a complex system with superstability) exhibited NIR‐II emission, as well as high photothermal conversion efficiencies of 82.9% and 65.1% under 532 and 980 nm laser irradiation, respectively. Therefore, this study can serve as a foundation for novel superradical studies and applications and the findings hold notable implications for radical stabilization, multifunctionalization, and structure–composition–property correlations.
{"title":"Nanocluster‐Stabilized Sulfur‐Based Superradical with High Photothermal Performance and NIR‐II Emission","authors":"Zhiyuan Hu, Shiyu Ji, Wenying Wang, Wanmiao Gu, Guowei Guan, Mingxing Chen, Qing You, Yue Zhou, Jian Cheng, Lingwen Liao, Nan Yan, Zhikun Wu","doi":"10.1002/anie.202517738","DOIUrl":"https://doi.org/10.1002/anie.202517738","url":null,"abstract":"The stabilization and multifunctionalization of radicals constitute two major challenges. We introduce a “kill two birds with one stone” methodology and illustrate the production of Au <jats:sub>64</jats:sub> (CPT) <jats:sub>31</jats:sub> S· from the newly obtained precursor nanocluster Au <jats:sub>64</jats:sub> (CPT) <jats:sub>32</jats:sub> (CPT: cyclopentanethiolate). Despite the isolated Au <jats:sub>64</jats:sub> (CPT) <jats:sub>31</jats:sub> S· are ultrastable (maintain the majority under 100 °C for 2 h in an atmospheric solution environment), they can initiate the polymerization of pentaerythritol triacrylate in 3D printing. In addition, the superradicial(which means it is not a single (super)atom but a complex system with superstability) exhibited NIR‐II emission, as well as high photothermal conversion efficiencies of 82.9% and 65.1% under 532 and 980 nm laser irradiation, respectively. Therefore, this study can serve as a foundation for novel superradical studies and applications and the findings hold notable implications for radical stabilization, multifunctionalization, and structure–composition–property correlations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"164 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731894","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}
Pub Date : 2025-12-13DOI: 10.1002/anie.2025-m0512055500
Ayan Chatterjee, Maximilian Schuler, Marius G. Braun, Christopher V. Synatschke, Qi Lu, Jiyao Yu, David Y.W. Ng, Tanja Weil
{"title":"Outside Front Cover: Regulating Promiscuous Catalysis via Substrate‐Induced Transient Assembly","authors":"Ayan Chatterjee, Maximilian Schuler, Marius G. Braun, Christopher V. Synatschke, Qi Lu, Jiyao Yu, David Y.W. Ng, Tanja Weil","doi":"10.1002/anie.2025-m0512055500","DOIUrl":"https://doi.org/10.1002/anie.2025-m0512055500","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"66 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731997","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}
Barbara Bogović, Ivana Colić, Ivana Nikšić‐Franjić, Vilko Smrečki, Ivanka Jerić
C ‐glycosylation is a well‐established strategy for improving the pharmacokinetic properties of peptides; however, the influence of chiral C ‐glycosyl amino acid incorporation on peptide conformation remains insufficiently explored. Most existing synthetic approaches restrict C ‐glycosyl amino acid placement to the N ‐terminus, C ‐terminus, or specific residues containing pre‐installed reactive groups. Here, we present a more versatile strategy based on the design and synthesis of customized C ‐glycosyl amino acids. Four variants bearing protected galactopyranose, ribofuranose, sorbofuranose, or allofuranose side chains were synthesized and incorporated into peptides using a solid‐phase methodology, enabling substitution at diverse sequence positions. Detailed NMR analyses revealed that each C ‐glycosyl α‐amino acid promotes distinct conformational preferences, primarily stabilized by hydrogen‐bonding networks between backbone amides and carbohydrate side chains. These findings uncover conformational information encoded within four non‐canonical C ‐glycosyl α‐amino acids, offering new molecular tools for catalysis, materials development and drug discovery.
C -糖基化是一种完善的策略，用于改善肽的药代动力学特性；然而，手性C -糖基氨基酸掺入对肽构象的影响仍未得到充分探讨。大多数现有的合成方法将C -糖基氨基酸的位置限制在N端、C端或含有预先安装的反应基团的特定残基上。在这里，我们提出了一种基于定制C -糖基氨基酸的设计和合成的更通用的策略。采用固相方法合成了四种带有受保护的半乳糖醛酸糖、核糖呋喃糖、山梨呋喃糖或己醛呋喃糖侧链的变体，并将其整合到肽中，实现了不同序列位置的取代。详细的核磁共振分析表明，每个C -糖基α -氨基酸促进不同的构象偏好，主要是通过主链酰胺和碳水化合物侧链之间的氢键网络来稳定。这些发现揭示了编码在四种非规范C -糖基α -氨基酸中的构象信息，为催化、材料开发和药物发现提供了新的分子工具。
{"title":"C ‐Glycosyl α‐Amino Acids as Structural Encoders of Peptide Conformation","authors":"Barbara Bogović, Ivana Colić, Ivana Nikšić‐Franjić, Vilko Smrečki, Ivanka Jerić","doi":"10.1002/anie.202522704","DOIUrl":"https://doi.org/10.1002/anie.202522704","url":null,"abstract":"<jats:italic>C</jats:italic> ‐glycosylation is a well‐established strategy for improving the pharmacokinetic properties of peptides; however, the influence of chiral <jats:italic>C</jats:italic> ‐glycosyl amino acid incorporation on peptide conformation remains insufficiently explored. Most existing synthetic approaches restrict <jats:italic>C</jats:italic> ‐glycosyl amino acid placement to the <jats:italic>N</jats:italic> ‐terminus, <jats:italic>C</jats:italic> ‐terminus, or specific residues containing pre‐installed reactive groups. Here, we present a more versatile strategy based on the design and synthesis of customized <jats:italic>C</jats:italic> ‐glycosyl amino acids. Four variants bearing protected galactopyranose, ribofuranose, sorbofuranose, or allofuranose side chains were synthesized and incorporated into peptides using a solid‐phase methodology, enabling substitution at diverse sequence positions. Detailed NMR analyses revealed that each <jats:italic>C</jats:italic> ‐glycosyl α‐amino acid promotes distinct conformational preferences, primarily stabilized by hydrogen‐bonding networks between backbone amides and carbohydrate side chains. These findings uncover conformational information encoded within four non‐canonical <jats:italic>C</jats:italic> ‐glycosyl α‐amino acids, offering new molecular tools for catalysis, materials development and drug discovery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"111 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732047","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}
The two-electron oxygen reduction reaction (2e– ORR) enables sustainable electrochemical production of hydrogen peroxide (H2O2), providing a green alternative to the traditional anthraquinone process. Herein, we report N/O dual-doped hierarchically porous carbon nanoreactors (N/O-HPCNs) derived from ZIF-8 via a facile one-step pyrolysis. The optimized catalyst achieves ∼90% H2O2 selectivity over a wide potential range in 0.10 M KOH. Crucially, in a flow cell, N/O-HPCNs deliver an industrial-grade current density of 200 mA cm−2 with 92.8% Faradaic efficiency and a remarkable H2O2 yield of 17.3 mol g−1 h−1, while maintaining > 80% Faraday efficiency for 100 h. Finite element simulations confirm that hierarchical pores enhance mass transfer and reduce H2O2 residence time, while DFT calculations elucidate the distinct roles of N doping for activity and oxygen functional groups in promoting 2e– ORR selectivity. This work provides a scalable strategy for sustainable H2O2 production.
双电子氧还原反应（2e - ORR）实现了过氧化氢（H2O2）的可持续电化学生产，为传统的蒽醌工艺提供了一种绿色替代方案。在这里，我们报道了通过简单的一步热解从ZIF-8中获得N/O双掺杂分层多孔碳纳米反应器（N/O- hpcns）。优化后的催化剂在0.10 M KOH的宽电位范围内实现了~ 90%的H2O2选择性。最关键的是，在流动电池中，N/O-HPCNs具有200 mA cm−2的工业级电流密度，具有92.8%的法拉第效率和17.3 mol g−1 h−1的H2O2产率，同时在100小时内保持>； 80%的法拉第效率。有限单元模拟证实了层次化孔隙增强了传质和减少H2O2停留时间，而DFT计算阐明了N掺杂对活性和氧官能团在促进2e - ORR选择性中的独特作用。这项工作为可持续生产H2O2提供了一种可扩展的策略。
{"title":"Industrial-Grade H2O2 Electrosynthesis via N/O-Doped Hierarchically Porous Carbon Nanoreactors with Remarkable Yield and Stability","authors":"Hongnan Du, Haitao Li, Huijuan Jing, Tianyi Liu, Zichen Xu, Chenyang Li, Yunyun Xu, Zijian Tan, Xiaolu Tang, Cheng Tang, Jian Liu, Zhong-Shuai Wu","doi":"10.1002/anie.202519013","DOIUrl":"https://doi.org/10.1002/anie.202519013","url":null,"abstract":"The two-electron oxygen reduction reaction (2e<sup>–</sup> ORR) enables sustainable electrochemical production of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), providing a green alternative to the traditional anthraquinone process. Herein, we report N/O dual-doped hierarchically porous carbon nanoreactors (N/O-HPCNs) derived from ZIF-8 via a facile one-step pyrolysis. The optimized catalyst achieves ∼90% H<sub>2</sub>O<sub>2</sub> selectivity over a wide potential range in 0.10 M KOH. Crucially, in a flow cell, N/O-HPCNs deliver an industrial-grade current density of 200 mA cm<sup>−2</sup> with 92.8% Faradaic efficiency and a remarkable H<sub>2</sub>O<sub>2</sub> yield of 17.3 mol g<sup>−1</sup> h<sup>−1</sup>, while maintaining > 80% Faraday efficiency for 100 h. Finite element simulations confirm that hierarchical pores enhance mass transfer and reduce H<sub>2</sub>O<sub>2</sub> residence time, while DFT calculations elucidate the distinct roles of N doping for activity and oxygen functional groups in promoting 2e<sup>–</sup> ORR selectivity. This work provides a scalable strategy for sustainable H<sub>2</sub>O<sub>2</sub> production.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"143 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729154","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 acidic media, electrocatalytic CO2 reduction to formic acid (HCOOH) represents a promising strategy for producing value-added chemicals. However, a critical challenge persists in enhancing CO2 adsorption and activation to suppress hydrogen evolution and boost product selectivity. Here, a Lewis acidic Zr-oxo cluster-rich porous confined structure decorated Bi2O2CO3 catalyst (Bi2O2CO3@PCN) is constructed via in situ electroreconstruction, which effectively promotes surface CO2 enrichment and K+ confinement in acidic conditions. Spatially adjacent Zr-oxo clusters enhance CO2 adsorption at the interface through Lewis acid-base interactions, facilitating the *OCHO intermediate formation. The optimized Bi2O2CO3@PCN catalyst achieves a high HCOOH Faradaic efficiency (FE) of 95% across a broad potential window and demonstrates a 5.9-fold higher mass activity compared to Bi2O2CO3 in acidic media at ‒1.8 V versus reversible hydrogen electrode. Notably, Bi2O2CO3@PCN exhibits superior HCOOH FE compared to Bi2O2CO3 under low-concentration CO2 flow. Mechanistically, the strong binding of CO2 molecules at Bi–O–Zr interfacial sites significantly lowers the hydrogenation barrier, while K+ enrichment repels protons and suppresses the hydrogen evolution reaction. This work underscores the pivotal role of surface confinement and Lewis acidic sites in regulating interfacial microenvironments and CO2 adsorption, highlighting their potential for efficient conversion of low-concentration CO2.
{"title":"Lewis Acid Adsorption Promotes CO2 Enrichment for Efficient Formic Acid Electrosynthesis on Reconstructed Bi2O2CO3 in Acidic Media","authors":"Chuan Hu, Ying Wang, Kang-Shun Peng, Xubei Wang, Yu-Jhih Shen, Kuiwei Yang, Feng Hu, Sung-Fu Hung, Yuping Wu, Seeram Ramakrishna, Shengjie Peng","doi":"10.1002/anie.202512476","DOIUrl":"https://doi.org/10.1002/anie.202512476","url":null,"abstract":"In acidic media, electrocatalytic CO<sub>2</sub> reduction to formic acid (HCOOH) represents a promising strategy for producing value-added chemicals. However, a critical challenge persists in enhancing CO<sub>2</sub> adsorption and activation to suppress hydrogen evolution and boost product selectivity. Here, a Lewis acidic Zr-oxo cluster-rich porous confined structure decorated Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> catalyst (Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>@PCN) is constructed via in situ electroreconstruction, which effectively promotes surface CO<sub>2</sub> enrichment and K<sup>+</sup> confinement in acidic conditions. Spatially adjacent Zr-oxo clusters enhance CO<sub>2</sub> adsorption at the interface through Lewis acid-base interactions, facilitating the *OCHO intermediate formation. The optimized Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>@PCN catalyst achieves a high HCOOH Faradaic efficiency (FE) of 95% across a broad potential window and demonstrates a 5.9-fold higher mass activity compared to Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> in acidic media at ‒1.8 V versus reversible hydrogen electrode. Notably, Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>@PCN exhibits superior HCOOH FE compared to Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> under low-concentration CO<sub>2</sub> flow. Mechanistically, the strong binding of CO<sub>2</sub> molecules at Bi–O–Zr interfacial sites significantly lowers the hydrogenation barrier, while K<sup>+</sup> enrichment repels protons and suppresses the hydrogen evolution reaction. This work underscores the pivotal role of surface confinement and Lewis acidic sites in regulating interfacial microenvironments and CO<sub>2</sub> adsorption, highlighting their potential for efficient conversion of low-concentration CO<sub>2</sub>.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"227 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729148","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}
Tao Yang, Fantao Kong, Min Li, Aiguo Kong, Xiangzhi Cui, Jianlin Shi
Developing new topological three-dimensional (3D) covalent organic framework (COF) structures with strong electron donor–acceptor (D–A) properties represents a promising approach for harvesting high-performance photocatalysts. In this study, we developed two unprecedented 3D COFs with sur-a topology by [3 + 2 + 4]-c strategy. The formation of sur-a topological structures relies on an elongated [3 + 2]-c tetrahedral thiazolo[5,4-d]thiazole (DTZ)-based building block (DTZ-CHO) with lower C2-symmetry. This unit is formed by inserting linear asymmetric DTZ subunit (2-c vertex) between two 3-c vertices. The incorporation of strong DTZ-pyrene/vinyl electron D–A structures efficiently promote exciton separation and charge transfer during photocatalysis, thereby demonstrating high-efficiency coupling photoactivation performance toward oxygen and biomass. It delivers a hydrogen peroxide photosynthesis rate of ∼12 092 µmol g−1 h−1 based on four-step direct Yeager-type oxygen photoreduction mechanism on DTZ active centers, pairing with efficient 5-hydroxymethylfurfural photooxidation (∼10 264 µmol g−1 h−1). This work highlights the potential of topologically unique 3D COFs with robust D-A structures as high-efficiency photocatalysts for artificial photosynthesis.
{"title":"Three-Dimensional Covalent Thiazolo[5,4-d]thiazole Frameworks with sur-a Topology for Coupling Photoactivation of Oxygen and Biomass","authors":"Tao Yang, Fantao Kong, Min Li, Aiguo Kong, Xiangzhi Cui, Jianlin Shi","doi":"10.1002/anie.202513616","DOIUrl":"https://doi.org/10.1002/anie.202513616","url":null,"abstract":"Developing new topological three-dimensional (3D) covalent organic framework (COF) structures with strong electron donor–acceptor (D–A) properties represents a promising approach for harvesting high-performance photocatalysts. In this study, we developed two unprecedented 3D COFs with <b>sur-a</b> topology by [3 + 2 + 4]-c strategy. The formation of <b>sur-a</b> topological structures relies on an elongated [3 + 2]-c tetrahedral thiazolo[5,4-d]thiazole (DTZ)-based building block (DTZ-CHO) with lower C<sub>2</sub>-symmetry. This unit is formed by inserting linear asymmetric DTZ subunit (2-c vertex) between two 3-c vertices. The incorporation of strong DTZ-pyrene/vinyl electron D–A structures efficiently promote exciton separation and charge transfer during photocatalysis, thereby demonstrating high-efficiency coupling photoactivation performance toward oxygen and biomass. It delivers a hydrogen peroxide photosynthesis rate of ∼12 092 µmol g<sup>−1</sup> h<sup>−1</sup> based on four-step direct Yeager-type oxygen photoreduction mechanism on DTZ active centers, pairing with efficient 5-hydroxymethylfurfural photooxidation (∼10 264 µmol g<sup>−1</sup> h<sup>−1</sup>). This work highlights the potential of topologically unique 3D COFs with robust D-A structures as high-efficiency photocatalysts for artificial photosynthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729147","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}
Malcolm R. P. George, Lobna A. Elsadek, Max Deering, Larissa Costa de Almeida, Jasper L. Tyler, Adam Noble, Valerie J. Paul, Hendrik Luesch, Craig P. Butts, Varinder K. Aggarwal
The unique potential of marine polyhydroxylated macrolides in chemical biology and drug discovery has long been constrained by their structural complexity and limited material availability, frustrating efforts in stereochemical assignment, synthesis, and mechanism‐of‐action elucidation. Here, we establish an integrated workflow, combining chemogenomic profiling, ultra‐high‐resolution NMR, and modular total synthesis, for the comprehensive functional and structural interrogation of this challenging natural product class. Applying this approach to caylobolides, natural products isolated from scarce samples of Okeania sp., we performed structure‐activity relationship studies revealing that acetylation at C29 markedly reduces both cytotoxicity and antifungal activity, pinpointing a key pharmacophore. Mechanistic profiling suggests that these macrolides disrupt membrane integrity, similar to amantelide A. Using natural compound samples, we simultaneously revised the structure of caylobolide B through 1 H, 1D‐selective TOCSY and HSQC NMR, and developed a modular fragment‐based synthesis of these compounds. By providing a unified methodology for genetic sensitivity profiling, precise structure and stereochemistry determination, and modular total synthesis, this work unlocks new opportunities for the discovery and rational design of potent marine‐derived therapeutics.
海洋多羟基大环内酯在化学生物学和药物发现方面的独特潜力长期受到其结构复杂性和有限的材料可用性的限制，在立体化学分配，合成和作用机制阐明方面的努力令人沮丧。在这里，我们建立了一个集成的工作流程，结合化学基因组分析、超高分辨率核磁共振和模块化全合成，对这类具有挑战性的天然产物进行全面的功能和结构分析。将这种方法应用于从稀有的Okeania sp.样品中分离的天然产物caylobolides，我们进行了结构-活性关系研究，揭示了C29的乙酰化显著降低了细胞毒性和抗真菌活性，确定了一个关键的药效团。机制分析表明，这些大环内酯类物质破坏了膜的完整性，类似于amantelide a .使用天然化合物样品，我们同时通过1h， 1D选择性TOCSY和HSQC NMR修改了caylobolide B的结构，并开发了基于模块化片段的合成这些化合物。通过提供遗传敏感性分析、精确结构和立体化学测定以及模块化全合成的统一方法，这项工作为发现和合理设计有效的海洋衍生疗法开辟了新的机会。
{"title":"Caylobolide B: Structure Revision, Total Synthesis, Biological Characterization, and Discovery of New Analogues","authors":"Malcolm R. P. George, Lobna A. Elsadek, Max Deering, Larissa Costa de Almeida, Jasper L. Tyler, Adam Noble, Valerie J. Paul, Hendrik Luesch, Craig P. Butts, Varinder K. Aggarwal","doi":"10.1002/anie.202523117","DOIUrl":"https://doi.org/10.1002/anie.202523117","url":null,"abstract":"The unique potential of marine polyhydroxylated macrolides in chemical biology and drug discovery has long been constrained by their structural complexity and limited material availability, frustrating efforts in stereochemical assignment, synthesis, and mechanism‐of‐action elucidation. Here, we establish an integrated workflow, combining chemogenomic profiling, ultra‐high‐resolution NMR, and modular total synthesis, for the comprehensive functional and structural interrogation of this challenging natural product class. Applying this approach to caylobolides, natural products isolated from scarce samples of <jats:italic>Okeania</jats:italic> sp., we performed structure‐activity relationship studies revealing that acetylation at C29 markedly reduces both cytotoxicity and antifungal activity, pinpointing a key pharmacophore. Mechanistic profiling suggests that these macrolides disrupt membrane integrity, similar to amantelide A. Using natural compound samples, we simultaneously revised the structure of caylobolide B through <jats:sup>1</jats:sup> H, 1D‐selective TOCSY and HSQC NMR, and developed a modular fragment‐based synthesis of these compounds. By providing a unified methodology for genetic sensitivity profiling, precise structure and stereochemistry determination, and modular total synthesis, this work unlocks new opportunities for the discovery and rational design of potent marine‐derived therapeutics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717444","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}
Sayad Doobary, Judith Braunreuther, Andrew K. Inge, Berit Olofsson
Densely functionalized alkenes are often utilized as excellent tools for further functionalization of molecules. Recent progress in their synthesis includes nucleophilic addition to vinylbenziodoxolones (VBX) and vinylbenziodoxoles (VBO) to reach alkenes with complete regio‐ and stereocontrol. In this work, we leverage the inherent properties of mechanochemistry to enable an efficient transition metal‐free one‐pot route to 1,2‐heteroatom‐substituted ( Z )‐alkenes directly from ethynylbenziodoxol(on)es (EBX/EBO), avoiding the isolation of VBX/VBO. We demonstrate a high‐yielding synthesis of a large variety of N/O/S ‐VBX reagents, which, combined with a telescoped nucleophilic addition, delivers a wide range of novel, complex ( Z )‐alkenes. This one‐pot strategy would be challenging to develop in solution due to a mismatch in reaction solvents, and the unique mechanochemical activation offered by solventless, solid‐state mixing also enables formation of products whose synthesis is inefficient with solvent‐based methods.
{"title":"Mechanochemical Synthesis of X ‐Vinylbenziodoxol(on)es and One‐Pot Conversion to Complex Alkenes **","authors":"Sayad Doobary, Judith Braunreuther, Andrew K. Inge, Berit Olofsson","doi":"10.1002/anie.202519049","DOIUrl":"https://doi.org/10.1002/anie.202519049","url":null,"abstract":"Densely functionalized alkenes are often utilized as excellent tools for further functionalization of molecules. Recent progress in their synthesis includes nucleophilic addition to vinylbenziodoxolones (VBX) and vinylbenziodoxoles (VBO) to reach alkenes with complete regio‐ and stereocontrol. In this work, we leverage the inherent properties of mechanochemistry to enable an efficient transition metal‐free one‐pot route to 1,2‐heteroatom‐substituted ( <jats:italic>Z</jats:italic> )‐alkenes directly from ethynylbenziodoxol(on)es (EBX/EBO), avoiding the isolation of VBX/VBO. We demonstrate a high‐yielding synthesis of a large variety of <jats:italic>N/O/S</jats:italic> ‐VBX reagents, which, combined with a telescoped nucleophilic addition, delivers a wide range of novel, complex ( <jats:italic>Z</jats:italic> )‐alkenes. This one‐pot strategy would be challenging to develop in solution due to a mismatch in reaction solvents, and the unique mechanochemical activation offered by solventless, solid‐state mixing also enables formation of products whose synthesis is inefficient with solvent‐based methods.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717442","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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