Chemistry - A European Journal最新文献

筛选
英文 中文
Olefin-Catalyzed Aromatic Bromination toward Biocompatible Tyrosine Modification. 烯烃催化芳香溴化制备生物相容性酪氨酸改性。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-27 DOI: 10.1002/chem.202501554
Riku Sakaguchi, Takuto Shimazu, Rakuto Yoshida, Tagui Nagano, Seijiro Matsubara, Daisuke Uraguchi, Keisuke Asano
{"title":"Olefin-Catalyzed Aromatic Bromination toward Biocompatible Tyrosine Modification.","authors":"Riku Sakaguchi, Takuto Shimazu, Rakuto Yoshida, Tagui Nagano, Seijiro Matsubara, Daisuke Uraguchi, Keisuke Asano","doi":"10.1002/chem.202501554","DOIUrl":"https://doi.org/10.1002/chem.202501554","url":null,"abstract":"<p><p>The chemical modification of biomolecules is an emerging technique for studying and manipulating biological mechanisms. Among these methodologies, catalysis offers advantages over stoichiometric strategies due to its ability to enhance selectivity, e.g., spatiotemporal control, via catalytic turnover, and the modification of tyrosine recently attracts considerable attention due to its significant biological functions. However, catalyst-controlled aromatic halogenation is challenging under near-physiological conditions due to the lack of biocompatible catalysts, despite the potential of tyrosine bromination as an attractive biomolecular labeling technique. In this study, inspired by the bioorthogonal reactivity of cyclic olefins, we developed catalytic aromatic bromination via the transfer of a bromenium ion from olefins to aromatic substrates based on the in-situ generation of bromiranium ions as active species. Bifunctional cyclooctenes bearing a hydroxybenzyl group efficiently catalyzed the bromination of phenol derivatives, which was applicable in tyrosine modification. The substituent effects of the catalysts primarily affected the rate of the generation of bromiranium ions, which provided the kinetics enabling light-gated catalysis that could be activated in situ via the photochemical deprotection of the hydroxybenzyl group. Such olefin catalysis was compatible with aqueous conditions, enabling the bromination of peptides, and the Lewis-base catalysis of the olefins proceeded even under acidic conditions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501554"},"PeriodicalIF":3.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148734","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Bistricyclic Aromatic Enes Containing Bifluorenylidene Units via Pd-Catalyzed Tandem Suzuki Coupling/Heck Cyclization Reaction. pd催化串联Suzuki偶联/Heck环化反应合成含双芴基的双环芳烃。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-27 DOI: 10.1002/chem.202501516
Luna Yang, Wangxuan Li, Shijie Gao, Hongchi Zhao, Yonggang Wu
{"title":"Synthesis of Bistricyclic Aromatic Enes Containing Bifluorenylidene Units via Pd-Catalyzed Tandem Suzuki Coupling/Heck Cyclization Reaction.","authors":"Luna Yang, Wangxuan Li, Shijie Gao, Hongchi Zhao, Yonggang Wu","doi":"10.1002/chem.202501516","DOIUrl":"https://doi.org/10.1002/chem.202501516","url":null,"abstract":"<p><p>A variety of bifluorenylidene-based bistricyclic aromatic enes (BAEs) and their derivatives have been prepared via the palladium-catalyzed Suzuki coupling/Heck cyclization tandem reaction in one pot. In the new scheme 2-bromophenyl trifluoromethanesulfonate and similar derivatives were chosen as one of reaction substrates, which could undergo tandem Suzuki coupling/Heck cyclization reaction with suitable arylboronic acid ester substrates to afford the expected BAEs and their derivatives. In the newly designed scheme, the raw materials are easier to obtain and can be applied to the synthesis of more BAEs and their derivatives.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501516"},"PeriodicalIF":3.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
In Situ X-ray Diffraction Studies on the Reduction of U3O8 by Various Reducing Agents. 不同还原剂还原U3O8的原位x射线衍射研究。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-27 DOI: 10.1002/chem.202500978
Marvin Michak, Frank-Constantin Ideker, Holger Kohlmann
{"title":"In Situ X-ray Diffraction Studies on the Reduction of U<sub>3</sub>O<sub>8</sub> by Various Reducing Agents.","authors":"Marvin Michak, Frank-Constantin Ideker, Holger Kohlmann","doi":"10.1002/chem.202500978","DOIUrl":"https://doi.org/10.1002/chem.202500978","url":null,"abstract":"<p><p>In situ X-ray diffraction studies were conducted to elucidate the reduction pathways of U<sub>3</sub>O<sub>8</sub> using various reducing agents, including hydrogen, the fluorinating agent polyvinylidene fluoride (PVDF), and calcium hydride (CaH<sub>2</sub>). The reduction processes were characterized by a transition from the orthorhombic, pseudo-hexagonal phase α-U<sub>3</sub>O<sub>8</sub> to the hexagonal polymorph, followed by the formation of fluorite-type UO<sub>2+x</sub> phases. The reduction temperature and intermediate phases vary with the type of reducing agent, though they all follow a similar sequence of phases. In the presence of pure hydrogen and upon reaction with PVDF and CaH<sub>2</sub>, U<sub>3</sub>O<sub>8</sub> transformed entirely into fluorite-type phases UO<sub>2+x</sub>. By decreasing the chemical potential of hydrogen via its partial pressure, the behavior of U<sub>3</sub>O<sub>8</sub> preceding the reduction to UO<sub>2+x</sub> can be switched from an orthorhombic-to-hexagonal phase transition followed by disproportionation to two different U<sub>3</sub>O<sub>8</sub> phases, presumably with different oxygen content, to a continuous oxygen loss within one U<sub>3</sub>O<sub>8</sub> phase without prior phase transition. The detailed analysis of lattice parameters and phase transformations in the course of the investigated reactions offers insights into the reduction pathways of uranium oxides, highlighting the impact of different reducing environments on the reaction pathways and final products.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500978"},"PeriodicalIF":3.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Revealing the Origin of Emission Quenching on Trivalent Europium β-Diketonate Complex Nanoparticles. 揭示三价β-二酮酸铕复合纳米粒子发射猝灭的起源。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-27 DOI: 10.1002/chem.202500952
Shunsuke Kobashi, Yoshinori Okayasu, Kohsuke Matsumoto, Osamu Tsutsumi, Yoichi Kobayashi
{"title":"Revealing the Origin of Emission Quenching on Trivalent Europium β-Diketonate Complex Nanoparticles.","authors":"Shunsuke Kobashi, Yoshinori Okayasu, Kohsuke Matsumoto, Osamu Tsutsumi, Yoichi Kobayashi","doi":"10.1002/chem.202500952","DOIUrl":"https://doi.org/10.1002/chem.202500952","url":null,"abstract":"<p><p>Eu(III) complex nanoparticles (NPs) prepared via reprecipitation exhibit characteristic emission in aqueous solutions without amphiphilic substituents, making them promising for bioimaging applications. However, although it is well established that water efficiently quenches emissions of Eu(III) complexes, reported emission quantum yields of water-soluble Eu(III) complex NPs vary significantly among studies, and the factors governing these emission properties have yet to be fully elucidated. In this study, we systematically investigated the emission quenching mechanisms of Eu(III) β-diketonate complex NPs by time-resolved absorption and emission spectroscopies. We found that the primary pathway is the interaction between coordinated and external water molecules, which strongly enhances nonradiative deactivation. Notably, coordinated water facilitates stronger interactions with the surrounding water, further promoting quenching. Additionally, we also found that aggregation causes emission quenching in Eu(III) complexes lacking phenyl groups in the β-diketonate moiety, which have smaller molecular volumes. These findings clarify the origin of luminescence variability in Eu(III) complex NPs and provide a foundation for rational material design to enhance luminescence stability in aqueous environments.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500952"},"PeriodicalIF":3.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Cover Feature: Asymmetric Total Synthesis of (+)- and (−)-Myrioneurinol Employing a “Resolutive” Late-Stage Barton-McCombie Deoxygenation 封面特征:采用“决定性”后期Barton-McCombie脱氧的(+)-和(−)-肉豆蔻油酚的不对称全合成
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-27 DOI: 10.1002/chem.202583003
Adrien Denizet, Rajesh Nomula, Richard Edwards, Patrick Y. Toullec, Philippe A. Peixoto
{"title":"Cover Feature: Asymmetric Total Synthesis of (+)- and (−)-Myrioneurinol Employing a “Resolutive” Late-Stage Barton-McCombie Deoxygenation","authors":"Adrien Denizet,&nbsp;Rajesh Nomula,&nbsp;Richard Edwards,&nbsp;Patrick Y. Toullec,&nbsp;Philippe A. Peixoto","doi":"10.1002/chem.202583003","DOIUrl":"https://doi.org/10.1002/chem.202583003","url":null,"abstract":"<p><b>Almost 50 years</b> after the first report of the so-called Barton–McCombie deoxygenation reaction, a resolutive version of this transformation has been developed by using a chiral chlorothionoformate-type reagent. The utility of this method was demonstrated by its late-stage application to access both enantiomers of myrioneurinol, a complex tetracyclic alkaloid. More information can be found in the Research Article by P. A. Peixoto# and co-workers (DOI: 10.1002/chem.202500267).\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 30","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202583003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effect of Chalcogen Interaction on the Structure of Methine-Bridged Trichalcogenophenes. 硫相互作用对甲烷桥接三氯基苯结构的影响。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-26 DOI: 10.1002/chem.202501123
Rio Nishimura, Ken-Ichi Yamashita
{"title":"Effect of Chalcogen Interaction on the Structure of Methine-Bridged Trichalcogenophenes.","authors":"Rio Nishimura, Ken-Ichi Yamashita","doi":"10.1002/chem.202501123","DOIUrl":"https://doi.org/10.1002/chem.202501123","url":null,"abstract":"<p><p>Polythienylenemethylidenes (PTMs) are promising conjugated polymers for organic electronics owing to their narrow bandgaps and extended π-conjugation. However, their stereochemistry remains unexplored. In this study, methine-bridged trithiophene and trifuran analogs were synthesized to investigate stereochemistry and chalcogen bonding effects. The compounds were obtained as mixtures of ZZ, EZ(=ZE), and EE geometric isomers, established through detailed NMR analyses. At thermal equilibrium, the ZZ isomer predominated in trithiophene (ZZ:(EZ+ZE):EE = 58:35:6), whereas trifuran showed a near-statistical distribution. X-ray crystallography revealed intramolecular S···S chalcogen bonding in trithiophene with S···S distances (≈3.04 Å) shorter than van der Waals radii and C-S···S angles of 171°. Comprehensive conformer searches and DFT calculations not only validated the higher stability of the ZZ isomer in trithiophene but also provided calculated isomer distributions that closely matched the experimental values. Multi-faceted computational analysis (ELF, NCI, QTAIM, and NBO) confirmed the presence of these chalcogen-centeredinteractions and quantified their strength through lone pair LP(S)→σ*(S-C) donor-acceptor orbital interactions. Trithiophene exhibited a unique dual-chalcogen bonding mode in the ZZ configuration. These findings elucidate the role of chalcogen bonding in stabilizing ZZ-trithiophenes and contribute to designing PTMs with controlled stereochemistry for organic electronics applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501123"},"PeriodicalIF":3.9,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144149024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Oxidative Dehydrogenation of N-Heteroaromatic Alkyl Alcohols and Amines Facilitated by Dearomative Tautomerization. 脱芳异变异构促进n -杂芳烷基醇和胺的氧化脱氢反应。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-26 DOI: 10.1002/chem.202501531
Omid Ghasemloo, Carson L Hasselbrink, Douglas D Cardona, Brenton DeBoef, Dugan Hayes
{"title":"Oxidative Dehydrogenation of N-Heteroaromatic Alkyl Alcohols and Amines Facilitated by Dearomative Tautomerization.","authors":"Omid Ghasemloo, Carson L Hasselbrink, Douglas D Cardona, Brenton DeBoef, Dugan Hayes","doi":"10.1002/chem.202501531","DOIUrl":"https://doi.org/10.1002/chem.202501531","url":null,"abstract":"<p><p>The oxidation of alcohols, amines, and halides is a fundamental transformation in organic chemistry with significant applications in the synthesis of fine chemicals, pharmaceuticals, and natural products. Here we show that a broad variety of N-heteroarenes bearing hydroxymethyl, aminomethyl, or halomethyl groups are oxidatively dehydrogenated to their respective aldehydes by simply heating them in acidic or basic aqueous solution under ambient atmosphere. The quantitative oxidation of 9-acridinemethanol to 9-acridinecarboxaldehyde serves as an illustrative example, proceeding to completion within 3 h in refluxing 5% aqueous acetic acid or even household vinegar. Quinoline derivatives may be similarly oxidized but require higher temperatures and longer reaction times, while indole derivatives are oxidized under basic conditions. Based on comprehensive regioselectivity screens, internal kinetic isotope competition, and density functional theory calculations, we propose a mechanism in which migration of a methylene hydrogen to the pyridinic nitrogen by acid-catalyzed dearomative tautomerization yields an unstable enol or enamine intermediate that then irreversibly loses two hydrogen atoms to atmospheric oxygen. In addition to the simplicity and environmentally benign nature of our method, we observe no indication of any over-oxidation to carboxylic acids. Finally, we demonstrate the synthetic utility of this reaction through two different one-pot formylations of acridine.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501531"},"PeriodicalIF":3.9,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Expanding the Scope of Mo(III) Precursor Molecules for Vapor Phase Growth of Mo-Based Materials: Mo(III) Guanidinate. 扩展Mo(III)前体分子在Mo基材料气相生长中的范围:Mo(III)胍。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-26 DOI: 10.1002/chem.202500244
Titel Jurca, Taylor M Currie, Alexander W Brodie, Diego R Javier-Jiménez, Bhumika Fnu, Justin Arami, Justin Moore, Seohui Lee, Glenn P A Yap, Lisa McElwee-White
{"title":"Expanding the Scope of Mo(III) Precursor Molecules for Vapor Phase Growth of Mo-Based Materials: Mo(III) Guanidinate.","authors":"Titel Jurca, Taylor M Currie, Alexander W Brodie, Diego R Javier-Jiménez, Bhumika Fnu, Justin Arami, Justin Moore, Seohui Lee, Glenn P A Yap, Lisa McElwee-White","doi":"10.1002/chem.202500244","DOIUrl":"https://doi.org/10.1002/chem.202500244","url":null,"abstract":"<p><p>The synthesis and characterization of tris(N,N'-di-isopropyl-2-dimethylamido-guanidinate)molybdenum(III), Mo(iPr-GND)3 is reported. This complex expands the known scope of tris(guanidinate)M(III) complexes to include Mo, and adds to the very limited knowledge of homoleptic mononuclear Mo(III) coordination complexes. Volatility of Mo(iPr-GND)3 is demonstrated via thermogravimetric analysis, hinting to potential applications as a molecular precursor for chemical vapor deposition (CVD) and atomic layer deposition (ALD). Proof of concept aerosol-assisted CVD growth with Mo(iPr-GND)3 as a single source precursor yielded MoCxNy films. Our results indicate a potential utility for Mo(iPr-GND)3 as a volatile precursor for ALD and CVD, with prospective use as a single-source precursor for growth of molybdenum nitrides and carbonitrides.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500244"},"PeriodicalIF":3.9,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144149029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Grafted Disulfide-linked Linear Polymers for Heterogeneous Thiyl Radical Photocatalysis. 非均相硫基自由基光催化的接枝二硫连接线性聚合物。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-25 DOI: 10.1002/chem.202500967
Sunil Kumar, Bolormaa Bayarkhuu, Jueun Park, Hong Y Cho, Jeehye Byun
{"title":"Grafted Disulfide-linked Linear Polymers for Heterogeneous Thiyl Radical Photocatalysis.","authors":"Sunil Kumar, Bolormaa Bayarkhuu, Jueun Park, Hong Y Cho, Jeehye Byun","doi":"10.1002/chem.202500967","DOIUrl":"https://doi.org/10.1002/chem.202500967","url":null,"abstract":"<p><p>Dynamic disulfide bonds offer a promising avenue for developing robust and reversible photocatalysts. This study introduces a novel polymer, Poly-SS, designed for heterogeneous thiyl radical photocatalysis, leveraging the dynamic nature of disulfide linkages. Poly-SS features linear disulfide-containing polymers grafted onto a polyvinyl backbone, combining the photoactivity of disulfide with the structural integrity of polyvinyl. This design facilitates efficient thiyl radical generation upon photoirradiation, enabling challenging organic transformations. Poly-SS demonstrates the exceptional photocatalytic efficiency for the aerobic oxidation of diarylalkynes to 1,2-diketones, achieving >99% conversion. The polyvinyl backbone plays a crucial role in maintaining polymer recyclability by promoting thiyl radical recombination and preserving disulfide linkages, addressing the inherent lability of molecular thiyl radicals. Furthermore, copolymerization with soluble monomer enhances the solubility of Poly-SS, enabling facile thin-film fabrication for diverse photoreactor designs. This work highlights a significant advancement in heterogeneous thiyl radical photocatalysis, showcasing the potential of carefully designed disulfide-linked polymers to overcome limitations associated with traditional molecular catalysts by integrating dynamic covalent chemistry with a robust polymer architecture.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500967"},"PeriodicalIF":3.9,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144141173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Innovative Cyclic Nucleotides - Nucleoside 2',3'-Seven Membered Cyclic Diphosphonate Derivatives. Theoretical Feasibility, Synthesis, and Properties. 创新环核苷酸-核苷2',3'-七元环二膦酸盐衍生物。理论可行性,合成和性质。
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-05-25 DOI: 10.1002/chem.202501228
Bilha Fischer, Sveta Liberman, Lea Bobot, Hadar T Ben Daniel, Dan T Major
{"title":"Innovative Cyclic Nucleotides - Nucleoside 2',3'-Seven Membered Cyclic Diphosphonate Derivatives. Theoretical Feasibility, Synthesis, and Properties.","authors":"Bilha Fischer, Sveta Liberman, Lea Bobot, Hadar T Ben Daniel, Dan T Major","doi":"10.1002/chem.202501228","DOIUrl":"https://doi.org/10.1002/chem.202501228","url":null,"abstract":"<p><p>7-membered cyclic nucleotides have remained unknown despite the natural abundance of their 5- and 6-membered counterparts. Here, we report the first synthesis of 2',3'-cyclic nucleosides (tetrathio)diphosphonate (2',3'-cNTDPs) by a rapid one-step, regioselective, and protection-free reaction of U, A, C, I, and G, with methylene-bis(1,3,2-dithia-phospholane-2-sulfide) (DTPS). The reaction proceeds instantaneously, even at -35 °C, resulting in the quantitative conversion of methylene-bis-DTPS. Density functional theory (DFT) calculations of ∆Gr confirm the synthetic feasibility and regioselectivity, attributing the efficiency to strain release in DTPS rings and entropic gain from thiirane elimination. The resulting 2',3'-cNTDPs exhibited remarkable hydrolytic stability and greater solution structural rigidity than free nucleosides.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202501228"},"PeriodicalIF":3.9,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144141297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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:481959085
Book学术官方微信