Angewandte Chemie International Edition最新文献

筛选
英文 中文
Quantifying the Biodegradation of Water‐Soluble Polymer Mixtures with Diffusion NMR Spectroscopy 用扩散核磁共振光谱定量水溶性聚合物混合物的生物降解
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-27 DOI: 10.1002/anie.202514235
Louisa T. Brenninkmeijer, Jacob L. Golding, Arianna Brandolese, Melanie M. Britton, Andrew P. Dove
{"title":"Quantifying the Biodegradation of Water‐Soluble Polymer Mixtures with Diffusion NMR Spectroscopy","authors":"Louisa T. Brenninkmeijer, Jacob L. Golding, Arianna Brandolese, Melanie M. Britton, Andrew P. Dove","doi":"10.1002/anie.202514235","DOIUrl":"https://doi.org/10.1002/anie.202514235","url":null,"abstract":"Polymers in liquid formulations result in 36 million tons of waste each year. It is estimated that 13% of these polymers directly enter, and accumulate in, natural environments, however, their fate is poorly understood; in part as a consequence of challenges in characterizing how the polymers biodegrade. Multiple analytical techniques have been used to quantify polymer biodegradation but require extensive sample preparation and can only measure one species accurately at a time, inhibiting the measurement of water‐soluble polymer mixtures. Here, we report the application of diffusion nuclear magnetic resonance spectroscopy as an alternative method to enable the facile monitoring of polymer biodegradation. This technique uniquely aids the understanding of biodegradation mechanisms, by measuring chemical as well as molar mass changes, concurrently, for both the polymer and degradation products. Furthermore, the ability to detect and measure the molar mass of multiple separate species enables the measurement of simultaneous biodegradation of polymer mixtures, including polymers with different chemical structures but the same molar mass.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":"e202514235"},"PeriodicalIF":16.6,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153645","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
Silylative Amide to Nitrile Conversion Mediated by Simple Lanthanide-Organoamides: Scope and Mechanism. 简单镧系有机酰胺介导的硅化酰胺制腈:范围和机理。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202513996
Zhiyu Feng,Qingheng Lai,Yuang Wang,Alessandro Motta,Yosi Kratish,Tobin J Marks
{"title":"Silylative Amide to Nitrile Conversion Mediated by Simple Lanthanide-Organoamides: Scope and Mechanism.","authors":"Zhiyu Feng,Qingheng Lai,Yuang Wang,Alessandro Motta,Yosi Kratish,Tobin J Marks","doi":"10.1002/anie.202513996","DOIUrl":"https://doi.org/10.1002/anie.202513996","url":null,"abstract":"Efficient, selective, and environmentally benign catalytic nitrile synthesis is attractive for pharmaceuticals, specialty chemicals and materials, and large-scale industrial applications. In this regard, metal-catalyzed silylative conversion of primary amides to nitriles is emerging as a promising approach. This contribution reports the utilization of readily available lanthanide-organic amido precatalysts, Ln[N(SiMe3)2]3, Ln = lanthanide, to selectively convert primary alkyl and aryl/heterocyclic amides having diverse functional groups to nitriles, including pharma building blocks, in high yields using the silane reagents PhSiH3 and TMS-O-[Si(H)(Me)-O-]n-TMS in a solvent-free process. Kinetic and mechanistic data reveal the role of lanthanide amidates as the catalytically-active species, while DFT analysis indicates a catalytic pathway unlike that found in transition metal complex-catalyzed processes. Thus, the lanthanide amidate resting state actively participates in the catalysis, where rate-determining bound amidate silylation is activated by the metal center and influenced by the bound amidate electronic and steric characteristics. DFT analysis of the catalytic cycle reveals that the relative energies of three intermediate endergonic steps, hence the rate-determining step, depends on the silane concentration.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":"e202513996"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140085","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
Laser-Programmed Spatial Relay Catalysis on Co─Ag Dual Heterojunctions for Efficient Nitrate-to-Ammonia Conversion via Migratory *NO2 Shuttling. Co - Ag双异质结的激光程序化空间接力催化通过迁移*NO2穿梭实现硝酸盐到氨的高效转化。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202515393
Jing Geng,Yaocai Wu,Sihan Ji
{"title":"Laser-Programmed Spatial Relay Catalysis on Co─Ag Dual Heterojunctions for Efficient Nitrate-to-Ammonia Conversion via Migratory *NO2 Shuttling.","authors":"Jing Geng,Yaocai Wu,Sihan Ji","doi":"10.1002/anie.202515393","DOIUrl":"https://doi.org/10.1002/anie.202515393","url":null,"abstract":"Electrocatalytic nitrate (NO3 -) reduction to ammonia (NH3) represents a sustainable strategy for wastewater treatment and green NH3 production; however, its efficiency is limited by sluggish reaction kinetics and the competing hydrogen evolution reaction (HER). Herein, we propose a laser-programmed spatial relay catalysis strategy mediated by migratory *NO2 intermediate on Co─Ag dual heterojunctions. Site-selective laser irradiation of Ag-predeposited Co foil generates spatially segregated interfaces, where hexagonal close-packed (hcp)-Co/face-centered cubic (fcc)-Co heterojunctions facilitate thermodynamically favorable NO3 - deoxygenation, and Ag/hcp-Co interfaces promote kinetically enhanced NO2 - protonation. Operando spectroscopic analysis, combined with electrochemical differential mass spectrometry (DEMS), confirms the migratory relay mechanism involving *NO2 transport between catalytic sites. Density functional theory (DFT) calculations show that interfacial charge redistribution enables distinct catalytic functions at interface sites. The phase-transformation-formed hcp-Co/fcc-Co heterojunctions enhance NO3 - adsorption and reduce deoxygenation barriers, whereas Ag/hcp-Co interfaces suppress HER and promote *NO hydrogenation by lowering the rate-determining *NO→*NOH barrier to 0.25 eV via Fermi-level d-band engineering. This collaborative spatial design reaches 94.8% ± 3.4% Faradaic efficiency (FE) for NH3 in nitrate-to-ammonia electroreduction at -0.4 V (versus RHE), with 92.5% activity retention over 50 cycles. It highlights the promise of interface-driven relay catalysis in complex electrochemical systems and enables scalable electrode fabrication.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"154 1","pages":"e202515393"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140384","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
Amyloid Peptide Nanofibrils Promote Efficient Neurotransmitter Oxidation and Serve as Scaffolds for Melanin Production. 淀粉样肽纳米原纤维促进有效的神经递质氧化并作为黑色素生成的支架。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202510234
Inhye Kim,Liam R Marshall,Shams Aaghaz,Yang Li,Ho Yee Joyce Fung,Ivan V Korendovych
{"title":"Amyloid Peptide Nanofibrils Promote Efficient Neurotransmitter Oxidation and Serve as Scaffolds for Melanin Production.","authors":"Inhye Kim,Liam R Marshall,Shams Aaghaz,Yang Li,Ho Yee Joyce Fung,Ivan V Korendovych","doi":"10.1002/anie.202510234","DOIUrl":"https://doi.org/10.1002/anie.202510234","url":null,"abstract":"We have shown that de novo designed peptides self-assemble in the presence of copper to create supramolecular assemblies capable of carrying out the oxidation of a range of neurotransmitters in the presence of dioxygen and hydrogen peroxide with high efficiency and in a sequence dependent manner. Moreover, these catalytic peptide assemblies are capable of templating melanin production. Guided by the structure activity relationships identified using the model systems we discovered that peptide assemblies formed by fragments of human carbonic anhydrase VII found in the brain also promote neurotransmitter degradation, supporting its role in neurodegenerative disease. Altogether, our results further support the role of metal-promoted catalysis in neurodegenerative disease and will facilitate development of new catalyst nanomaterials capable of promoting oxidative transformation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"93 1","pages":"e202510234"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140383","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
Fluorescent Peptide Tracers for Simultaneous Oxytocin Receptor Activation and Visualization. 同时催产素受体激活和可视化的荧光肽示踪剂。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-26 DOI: 10.1002/anie.202515180
Monika Perisic Böhm,Predrag Kalaba,Rachel S Gormal,Maja Zupančič,Alexandra Wolf,Mia Juračić,Thomas Kremsmayr,Frédéric A Meunier,Thierry Langer,Christian W Gruber,Erik Keimpema,Markus Muttenthaler
{"title":"Fluorescent Peptide Tracers for Simultaneous Oxytocin Receptor Activation and Visualization.","authors":"Monika Perisic Böhm,Predrag Kalaba,Rachel S Gormal,Maja Zupančič,Alexandra Wolf,Mia Juračić,Thomas Kremsmayr,Frédéric A Meunier,Thierry Langer,Christian W Gruber,Erik Keimpema,Markus Muttenthaler","doi":"10.1002/anie.202515180","DOIUrl":"https://doi.org/10.1002/anie.202515180","url":null,"abstract":"The oxytocin receptor (OTR) regulates critical physiological functions and has been implicated in a range of diseases, including psychiatric and neurodevelopmental disorders such as autism spectrum disorder. However, a lack of reliable molecular tools hampers the progress in understanding OTR's mechanistic roles in (patho)physiological processes. In this work, we addressed this gap and developed potent, selective, and bright fluorescent peptide tracers that enable precise spatial and functional investigations of OTR actions. Our tracers showed efficient OTR labeling, activation, and internalization in cellular bioassays in both live and fixed overexpression and primary cell systems, including those subjected to immunocytochemical protocols, highlighting their versatility as reliable new imaging tools. Additionally, they facilitated single-molecule tracking of OTR with live-cell super-resolution microscopy and were able to separate OTR-positive cells from mixed oxytocin and vasopressin receptor-containing cell populations via fluorescence-activated cell sorting, underscoring their wider scope for live-cell applications. In summary, we developed versatile fluorescent tracers based on the endogenous ligand oxytocin for both live-cell and post-hoc imaging that have additional functional capabilities beyond traditional antibody labeling, offering new avenues to explore OTR's role in health and disease.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":"e202515180"},"PeriodicalIF":16.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140087","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
Failure Mechanism of High-Temperature Li–S Batteries in Localized High-Concentration Electrolytes 局部高浓度电解液中高温锂硫电池失效机理研究
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202515993
Zixiong Shi, Simil Thomas, Georgian Melinte, Dong Guo, Jehad K. El-Demellawi, Nizar Jaber, Manuel A. Quevedo-Lopez, Osman M. Bakr, Omar F. Mohammed, Husam N. Alshareef
{"title":"Failure Mechanism of High-Temperature Li–S Batteries in Localized High-Concentration Electrolytes","authors":"Zixiong Shi, Simil Thomas, Georgian Melinte, Dong Guo, Jehad K. El-Demellawi, Nizar Jaber, Manuel A. Quevedo-Lopez, Osman M. Bakr, Omar F. Mohammed, Husam N. Alshareef","doi":"10.1002/anie.202515993","DOIUrl":"https://doi.org/10.1002/anie.202515993","url":null,"abstract":"Conventional ether-based electrolytes struggle to sustain steady operation of lithium–sulfur (Li–S) batteries at high temperatures due to inferior thermal durability and aggravated parasitic reactions. Although localized high-concentration electrolyte (LHCE) has emerged as a promising strategy to enhance thermal stability, its deployment in high-temperature (HT) Li–S batteries has met with limited success. Herein, the failure mechanism of HT Li–S batteries in LHCE is revealed via probing sulfur redox reactions and electrolyte solvation chemistry. Slow reaction kinetics and high polysulfide reactivity are determined to be the dominant factors causing the rapid capacity deterioration at high temperatures. To this end, a diethylene glycol dibutyl ether-based localized medium concentration electrolyte (B-LMCE) with suitable anion concentration and weakly solvating effect is developed. The new electrolyte concurrently achieves fast cathode kinetics and stable anode/electrolyte interface. With the assistance of a tailored electrochemical voltage range of 1–3.8 V, Li–S batteries sustain a durable cycling performance over 250 cycles at 60 °C. They also showcase superior wide-temperature operation (0 °C–80 °C) while enabling feasible fabrication of Ah-level pouch cells. Our study opens a new avenue for designing extreme-temperature electrolytes toward pragmatic Li–S batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":"e202515993"},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141083","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
Sulfinyl Aziridines as Stereoselective Covalent Destabilizing Degraders of the Oncogenic Transcription Factor MYC 亚砜酰叠氮嘧啶作为致癌转录因子MYC的立体选择性共价不稳定降解剂
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202508518
Hannah T. Rosen, Kelvin Li, Christian E. Stieger, Erin L. Li, Brynne Currier, Scott M. Brittain, Francisco J. Garcia, Diana C. Beard, Michael D. Jones, Sandra Haenni-Holzinger, Dustin Dovala, Jeffrey M. McKenna, Markus Schirle, Thomas J. Maimone, Daniel K. Nomura
{"title":"Sulfinyl Aziridines as Stereoselective Covalent Destabilizing Degraders of the Oncogenic Transcription Factor MYC","authors":"Hannah T. Rosen, Kelvin Li, Christian E. Stieger, Erin L. Li, Brynne Currier, Scott M. Brittain, Francisco J. Garcia, Diana C. Beard, Michael D. Jones, Sandra Haenni-Holzinger, Dustin Dovala, Jeffrey M. McKenna, Markus Schirle, Thomas J. Maimone, Daniel K. Nomura","doi":"10.1002/anie.202508518","DOIUrl":"https://doi.org/10.1002/anie.202508518","url":null,"abstract":"Although MYC is a significant oncogenic transcription factor driver of cancer, directly targeting MYC has remained challenging due to its intrinsic disorder and poorly defined structure, deeming it “undruggable.” Whether transient pockets formed within unstructured regions of proteins can be selectively targeted with small molecules remains an outstanding challenge. Here, we developed a stereochemically paired spirocyclic oxindole aziridine covalent library and screened this library for degradation of MYC. We identified a hit covalent ligand, KL2-236, bearing a unique sulfinyl aziridine warhead, that engaged MYC as a pure MYC/MAX protein complex, and in cancer cells to destabilize MYC, inhibit MYC transcriptional activity and degrade MYC in a proteasome-dependent manner through targeting intrinsically disordered C203 and D205 residues. Notably, this reactivity was most pronounced for specific stereoisomers of KL2-236 with a diastereomer, KL4-019, that was largely inactive. Mutagenesis of both C203 and D205 completely attenuated KL2-236-mediated MYC degradation. We also optimized our KL2-236 hit compound to generate a more potent, selective, and durable MYC degrader, KL4-219A. Our results reveal a novel ligandable site within MYC and indicate that certain intrinsically disordered regions within transcription factors, such as MYC, can be interrogated by isomerically unique chiral small molecules, leading to destabilization and degradation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"107 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141114","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
Enhanced Efficiency and Stability of Inverted Perovskite Solar Cells via Isomerization Engineering of Self-Assembled Monolayers. 通过自组装单层异构化工程提高倒置钙钛矿太阳能电池的效率和稳定性。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202513338
Chao Lv,Yawei Miao,Jing Wang,Jiayu Li,Zeyuan Hu,Yuexing Zhang,Ping Wu,Longlong Geng,Ying Li,Xiangchuan Meng,Fariba Tajabadi,Nima Taghavinia,Ke Gao,Qifan Xue
{"title":"Enhanced Efficiency and Stability of Inverted Perovskite Solar Cells via Isomerization Engineering of Self-Assembled Monolayers.","authors":"Chao Lv,Yawei Miao,Jing Wang,Jiayu Li,Zeyuan Hu,Yuexing Zhang,Ping Wu,Longlong Geng,Ying Li,Xiangchuan Meng,Fariba Tajabadi,Nima Taghavinia,Ke Gao,Qifan Xue","doi":"10.1002/anie.202513338","DOIUrl":"https://doi.org/10.1002/anie.202513338","url":null,"abstract":"Carbazole-based SAMs show great promise as interfacial modifiers in inverted perovskite solar cells (PSCs). Their large dipole moments and covalent binding capabilities suppress charge recombination and enhance device stability. We designed two isomeric carbazole SAMs (EPACz and PPACz) by adjusting the phenyl ring position. PPACz exhibits a higher dipole moment (2.60 D versus 1.77 D for EPACz) and a narrower HOMO-LUMO gap (2.39 eV), enabling superior hole extraction. PPACz-based devices achieved an excellent PCE of 26.1% (versus 22.0% for EPACz), with 23.5% efficiency for 1 cm2 devices. The stronger tridentate anchoring of PPACz to ITO (compared with EPACz) improves interfacial stability. Unencapsulated devices retained over 90% of their initial efficiency after 540 h, demonstrating exceptional durability. This work provides key insights for designing high-performance SAMs in perovskite photovoltaics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"38 1","pages":"e202513338"},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134054","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
Synthesis of Bridge-Substituted Bicyclo[1.1.1]Pentanes by Catalytic Metal Carbene Insertion into Bicyclo[1.1.0]Butanes 催化金属卡宾插入双环[1.1.0]丁烷合成桥取代双环[1.1.1]戊烷
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202514232
Shaopeng Liu, Yongquan Ning, Wei Song, Paramasivam Sivaguru, Yixuan Wang, Ying Gan, Edward A Anderson, Xihe Bi
{"title":"Synthesis of Bridge-Substituted Bicyclo[1.1.1]Pentanes by Catalytic Metal Carbene Insertion into Bicyclo[1.1.0]Butanes","authors":"Shaopeng Liu, Yongquan Ning, Wei Song, Paramasivam Sivaguru, Yixuan Wang, Ying Gan, Edward A Anderson, Xihe Bi","doi":"10.1002/anie.202514232","DOIUrl":"https://doi.org/10.1002/anie.202514232","url":null,"abstract":"1,2,3-Trisubstituted bicyclo[1.1.1]pentanes (BCPs) are emerging saturated hydrocarbon bioisosteres for polysubstituted benzenes; however, their synthesis from bicyclo[1.1.0]butanes (BCBs) via direct metal carbene insertion remains unrealized. Herein, we report the first catalytic metal carbene insertion into BCBs using triftosylhydrazones as safe and stable carbene precursors, which circumvents the use of [1.1.1]propellane in the synthesis of the BCPs scaffold. This operationally straightforward method accommodates a wide range of substituted BCB esters and triftosylhydrazones, enabling the synthesis of valuable 1,2,3-trisubstituted BCPs, including those bearing a trifluoromethylated quaternary all-carbon center, in good-to-excellent yields. Selective post-synthetic transformations of the product BCP esters into other useful small-ring building blocks, as well as the preparation of the BCP analogue of a drug molecule fragment, demonstrate the versatility and utility of this chemistry. Mechanistic investigations, including density functional theory calculations, support a direct, stepwise metal carbene addition into the C─C bond of the BCB.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"95 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134490","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
trans-Silaboration of Terminal Alkynes Enabled by Development of a New Si─B Reagent 一种新型Si─B试剂的开发促进了末端炔的反硅化反应
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-09-25 DOI: 10.1002/anie.202517688
Song Chen, Kailin Yin, Liangbo Zhu, Chunming Cui, Dongbing Zhao
{"title":"trans-Silaboration of Terminal Alkynes Enabled by Development of a New Si─B Reagent","authors":"Song Chen, Kailin Yin, Liangbo Zhu, Chunming Cui, Dongbing Zhao","doi":"10.1002/anie.202517688","DOIUrl":"https://doi.org/10.1002/anie.202517688","url":null,"abstract":"The 1,2-silaboration of alkynes is a powerful strategy for regio- and stereoselective yielding versatile 1-boryl-2-silyl alkenes, which are ubiquitous synthons leveraging the orthogonal reactivity of boron and silicon for diverse downstream transformations. However, it dominantly features <i>cis</i>-selectivity. <i>trans</i>-Selective silaboration remains underdeveloped to date, especially for sterically hindered terminal alkynes. Herein, we report a Pd-catalyzed <i>trans</i>-silaboration of terminal alkynes using a novel Si─B reagent, TBSQ, bearing an 8-quinolinyl directing group on silicon. This strategy provides exclusive <i>E</i>-selectivity across a broad substrate scope, including bulky alkynes. Mechanistic studies suggest a combined <i>cis</i>-addition/Z→E isomerization pathway, with the directing group playing a crucial role. The resulting <i>trans</i>-1-boryl-2-silyl alkenes serve as valuable building blocks for selective downstream functionalization toward pharmaceutically relevant molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":"e202517688"},"PeriodicalIF":16.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141087","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
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
相关产品
×
本文献相关产品
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信