Tetrahedron最新文献_第5页

Oxa-phenalene [b]-fused BODIPY dyes: Synthesis, structures, and photophysical properties Oxa-phenalene [b]-熔融BODIPY染料：合成、结构及光物理性质

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-16 DOI: 10.1016/j.tet.2025.134728

Hao Guan , Ruihan Yang , Limin He , Xin Li , Yiming Cao , Shulin Gao , Yanni Li , Yanhua Yang , Xiangguang Li

{"title":"Oxa-phenalene [b]-fused BODIPY dyes: Synthesis, structures, and photophysical properties","authors":"Hao Guan , Ruihan Yang , Limin He , Xin Li , Yiming Cao , Shulin Gao , Yanni Li , Yanhua Yang , Xiangguang Li","doi":"10.1016/j.tet.2025.134728","DOIUrl":"10.1016/j.tet.2025.134728","url":null,"abstract":"<div><div>Conventional BODIPY dyes exhibit narrow absorption and emission bands in the visible spectrum, limiting their utility in near-infrared (NIR) applications. Addressing this challenge—designing BODIPY-based NIR fluorophores with broad spectral features—requires strategic π-conjugation extension and heteroatom fusion. In this work, we synthesized four novel oxa-phenalene [<em>b</em>]-fused BODIPY dyes (<strong>OFB-1</strong>–<strong>OFB-4</strong>) via regioselective nucleophilic aromatic substitution and palladium-catalyzed intramolecular Heck coupling, starting from mono- or dichloro-BODIPY precursors and 1-hydroxy-8-bromonaphthalene. The fused oxa-phenalene unit enforces exceptional coplanarity within the BODIPY core, driving substantial bathochromic shifts into the NIR region. The bis-fused derivative, <strong>OFB-2</strong>, achieves absorption and emission maxima at 707 nm and 725 nm, respectively. Remarkably, the mono-fused derivative <strong>OFB-1</strong> exhibits dual absorption bands with a full-width at half-maximum (FWHM) of 102 nm, a hallmark of intramolecular charge transfer (ICT) effects. Electronic structure analysis reveals that oxa-phenalene [<em>b</em>] fusion uniquely modulates the frontier molecular orbitals: it minimally impacts the LUMO energy level but significantly elevates the HOMO energy level, thereby narrowing the HOMO–LUMO gap. This contrasts sharply with traditional [<em>b</em>]-fused BODIPYs, where π-extension typically reduces LUMO levels. The selective HOMO elevation in oxa-phenalene-fused systems highlights its potential for tailoring optoelectronic properties while retaining desirable electron-transport characteristics.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"183 ","pages":"Article 134728"},"PeriodicalIF":2.1,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144099727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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Process development and optimization of apalutamide synthesis aided by the Design of Experiments (DoE) 实验设计辅助下阿帕鲁酰胺合成工艺的开发与优化

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-15 DOI: 10.1016/j.tet.2025.134725

Hailong Wang , Lijun Li , Fubin Yang , Dongming Li , Shuming Wu , Wei Yan , Guodong Sun , Jie Tan , Yishao Li , Hua Yang , Zhongqing Wang

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Recent synthetic strategies for the direct C–H activation radiofluorination and radioiodination of aromatic systems 芳烃系直接碳氢活化、放射性氟化和放射性碘化的合成新策略

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-15 DOI: 10.1016/j.tet.2025.134727

Wenshu Wang , Yuting Yan , Jianhui Huang

{"title":"Recent synthetic strategies for the direct C–H activation radiofluorination and radioiodination of aromatic systems","authors":"Wenshu Wang , Yuting Yan , Jianhui Huang","doi":"10.1016/j.tet.2025.134727","DOIUrl":"10.1016/j.tet.2025.134727","url":null,"abstract":"<div><div>Radiopharmaceuticals are crucial for diagnostic imaging and targeted therapies due to their specificity and high therapeutic effectiveness, have attracted much attention in the field of biomedical sciences. Radiopharmaceuticals consist of radionuclides and drugs, and the radionuclides can be classified as metalic and nonmetalic radionuclides. Among nonmetallic radioisotopes, radiofluorine and radioiodines are the most commonly used halogen sources. Radiolabeling as an approach introducing radionuclides to the pharmaceutical active reagents have been well developed in recent years. Among these radionuclide labeling methods, C–H direct radiofluorination and radioiodination of alkyl- and arene- containing molecules have been developed in fast, simple and convenient transformation, which starting from readily available precursors, and have provided new potential in radiopharmaceutical synthesis. In this review, we have summarized the advanced strategies and the applications of direct C–H radiofluorination and radioiodination methodologies over the past few years. Overall, these methods have broadened the development space with the integration of new technologies.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"183 ","pages":"Article 134727"},"PeriodicalIF":2.1,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144084397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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Synthesis of 2′,2′-dibromovinyl porphyrins and their versatile use in Pd-catalyzed cross-coupling reactions 2′，2′-二溴酰基卟啉的合成及其在pd催化交叉偶联反应中的广泛应用

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-14 DOI: 10.1016/j.tet.2025.134704

Hasrat Ali, Johan E. van Lier

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Visible light photoredox catalyzed hydrophosphinylation of unactivated alkenes 可见光光氧化还原催化非活化烯烃氢膦化反应

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-14 DOI: 10.1016/j.tet.2025.134712

Ming Qi, An-Wu Xu

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Recent synthetic methodology advancements towards all-carbon quaternary center formation and applications 全碳四元中心合成方法及应用进展

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-14 DOI: 10.1016/j.tet.2025.134711

Taotao Ling, Jose M. Garfias, Sydney L. Lawson, Fatima Rivas

{"title":"Recent synthetic methodology advancements towards all-carbon quaternary center formation and applications","authors":"Taotao Ling, Jose M. Garfias, Sydney L. Lawson, Fatima Rivas","doi":"10.1016/j.tet.2025.134711","DOIUrl":"10.1016/j.tet.2025.134711","url":null,"abstract":"<div><div>The synthesis of organic molecules through regioselective and enantioselective processes represents a significant challenge in organic chemistry, but constructing molecules with all-carbon quaternary centers poses even greater complexity. The importance of synthetic organic chemistry in daily life cannot be overstated, as organic molecules are fundamental to human existence - from the nutrients that sustain us to the pharmaceutical products that maintain our health. Fundamental knowledge on chemical reactivity, particularly that of carbon-carbon bond formation in sterically hindered substrates, is of great interest in developing and studying new chemical matter. Increases in precision medicine have also highlighted the importance of molecular selectivity towards biological targets and the need to access complex molecular scaffolds with unique stereochemistry features such as quaternary carbon centers. The scarcity of molecules containing all-carbon quaternary centers has constrained our ability to fully explore their properties. This report examines recent methodological advances since 2019 in their synthesis, focusing on three key synthetic approaches: single electron transfer (SET) mediated reactions, reactions mediated by chemical phenomena associated with charge separation (electrochemistry), Lewis acid and transition metal mediated cyclization/rearrangement reactions. These innovative synthetic strategies open new pathways for creating complex chemical structures, advancing our ability to develop both novel therapeutic candidates and new materials. The enhanced efficiency of these approaches enables the exploration of increasingly sophisticated molecular architectures, expanding opportunities for discovering compounds with unique biological activities and material properties.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"183 ","pages":"Article 134711"},"PeriodicalIF":2.1,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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Synthetic studies towards (−)-plicatic acid: A Ni-catalyzed reductive cyclization strategy for the construction of its aryltetralin framework （−）-塑胶酸的合成研究：镍催化还原环化策略构建芳基四氢萘骨架

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-14 DOI: 10.1016/j.tet.2025.134724

Xiao-Wei Cong , Yu Peng

引用次数: 0

Bridged N–based ionic liquid and their application in synthesis of five membered N–heterocycles 桥接n基离子液体及其在五元n杂环合成中的应用

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-14 DOI: 10.1016/j.tet.2025.134721

Anvita Chaudhary, Richa Srivastava

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N-Bromo-N-fuorobenzenesulfonylamide (BFBSA) – A newly developed reagent for the bromination of (Het)arenes, drugs and natural products under mild conditions n -溴- n -呋喃苯磺酰酰胺（BFBSA）是一种新开发的在温和条件下溴化（Het）芳烃、药物和天然产物的试剂

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-13 DOI: 10.1016/j.tet.2025.134723

Chaolin Li, Xianjin Yang

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Synthesis of quinoline liquid crystals by inverse electron demand Diels-Alder cycloaddition 反电子需求Diels-Alder环加成法合成喹啉液晶

IF 2.1 3区化学

Tetrahedron Pub Date : 2025-05-13 DOI: 10.1016/j.tet.2025.134722

Luma Fritsch , Sidnei Moura e Silva , Luis A. Baptista , Richard J. Mandle , Aloir A. Merlo

{"title":"Synthesis of quinoline liquid crystals by inverse electron demand Diels-Alder cycloaddition","authors":"Luma Fritsch , Sidnei Moura e Silva , Luis A. Baptista , Richard J. Mandle , Aloir A. Merlo","doi":"10.1016/j.tet.2025.134722","DOIUrl":"10.1016/j.tet.2025.134722","url":null,"abstract":"<div><div>Tetrahydroquinolines (THQ) cycloadducts, as well as their oxidation to the corresponding quinolines are reported. THQs were achieved through the Inverse Electron Demand [4 + 2]-Diels–Alder (IEDDA) cycloaddition. The [4 + 2]-IEDDA cycloadducts were obtained through a three-component reaction involving aromatic aldehydes, amines and pyrano dienophile, in the presence of TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperydine-1-oxyl), trifluoroacetic acid and acetonitrile, in low yields <40 %. Theoretical studies were complimentary performed to analyze the chemical reactivity, regio- and stereoselectivity of the IEDDA cycloaddition. The preference for the formation of the THQs cycloadducts was dictated by frontier orbital molecular (FOMs) LUMO of 2-azadieno and HOMO of the dienophile. Oxidation of the THQs with DDQ yielded quinolines in high yields >90 %. The thermal behavior of the THQs and quinolines was studied using DSC and POM techniques. The final quinolines exhibited an amorphous appearance with vitreous, glossy, and brittle characteristics. Through POM studies only one quinoline displayed stable liquid crystal behavior with a glass transition temperature (Tg) and glassy nematic mesophase at room temperature was assigned, without no thermal decomposition detected after cycles of heating and cooling.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"183 ","pages":"Article 134722"},"PeriodicalIF":2.1,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144070828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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