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Regioselective and Diastereoselective (5+1)-Annulations: Access to Functionalized Hexahydroisoindoles from Morita–Baylis–Hillman Carbonates and 3-Aryl-3-Oxopropanenitriles 区域选择性和非对映选择性(5+1)-环:从森田-贝利斯-希尔曼碳酸盐和3-芳基-3-氧丙烷腈中获得功能化六氢异吲哚
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-02-05 DOI: 10.1002/ejoc.70323
Rongzhen Li, Xuling Chen, Pengfei Li
Moving beyond classical Morita–Baylis–Hillman (MBH) carbonates, we have developed novel pyrrolidinone-based MBH carbonates. Owing to their dielectrophilic nature, these compounds serve as versatile C5 synthons in annulation reactions. Herein, we report their (5+1)-annulations with 3-aryl-3-oxopropanenitriles, which efficiently deliver functionalized hexahydroisoindoles using 1,8-diazabicyclo[5.4.0]undec-7-ene as a bifunctional nucleophilic/base catalyst. This synthetic strategy enables the asymmetric synthesis of hexahydroisoindoles with good regioselectivity and diastereoselectivity.
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引用次数: 0
Conference Report: Journées De Chimie Supramoléculaire 2025 Strasbourg, May 22–23, 2025 会议报告:Journees De Chimie Supramoleculaire 2025斯特拉斯堡,2025年5月22 - 23日
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-02-04 DOI: 10.1002/ejoc.70297
Irene Regeni
The JCS 2025 – Journées de Chimie Supramoléculaire – conference was held in Strasbourg on May 22–23, 2025. This conference report highlights the activities of the Supramolecular Chemistry group of the French Chemical Society and showcases emerging themes in the field.
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引用次数: 0
Consecutive (Pseudo-)Four-Component Synthesis of Meta- and Ortho-Biaryl Triarylamines with Tunable Emission and Redox Properties 具有可调发射和氧化还原性质的间、邻联芳基三芳胺的连续(伪)四组分合成
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-02-04 DOI: 10.1002/ejoc.70312
Regina Kohlbecher, Tim Lippert, Hendrik Schröder, Dustin N. Jordan, Christoph Janiak, Thomas J. J. Müller
The strategic combination of Suzuki coupling and Buchwald–Hartwig amination in consecutive (pseudo-)four-component syntheses provides a highly efficient and modular route to meta- and ortho-biaryl-substituted triarylamines (m- and o-bTAA), thereby expanding a substance library that has previously focused on para-bTAA. The broad range of novel bTAA enables comprehensive investigations of their electronic properties and reveals highly tunable emission in solution from blue to yellow, with quantum yields up to 55%, and up to 26% in the solid state. The bTAA also show strong potential as stimulus-responsive luminophores due to their pronounced positive emission solvatochromism, which indicates substantial charge transfer character—particularly in the m-bTAA—as well as aggregation-induced emission in DMSO/water mixtures with with intensity enhancements of up to 75-fold. Quantitative 2D Hammett correlations combined with quantum-chemical calculations systematically rationalize substituent effects not only on the emission properties but also on the low, reversible redox potentials determined by cyclic voltammetry. Cyclic voltammetry further reveals irreversible dimerization processes in certain unsubstituted bTAA. In addition to para-substituents, the biaryl substitution pattern (meta, ortho, or para) also proves to be a finely tunable parameters, opening new opportunities for the rational design of tailored bTAA emitters with predictable structure–property relationships.
Suzuki偶联和Buchwald-Hartwig胺化在连续(伪)四组分合成中的战略组合为间和邻二芳基取代三芳胺(m-和o-bTAA)提供了高效和模块化的途径,从而扩展了以前专注于对btaa的物质库。广泛的新型bTAA能够全面研究其电子特性,并在溶液中显示从蓝色到黄色的高度可调发射,量子产率高达55%,在固态中高达26%。由于bTAA具有明显的正发射溶剂致色性,bTAA也显示出作为刺激响应发光团的强大潜力,这表明了大量的电荷转移特性,特别是在m-bTAA中,以及DMSO/水混合物中聚集诱导的发光,其强度增强高达75倍。定量二维哈米特关联结合量子化学计算系统地合理化取代基效应,不仅对发射性质,而且对低,可逆的氧化还原电位由循环伏安法确定。循环伏安法进一步揭示了某些未取代bTAA的不可逆二聚化过程。除了对取代基,联芳基取代模式(元、邻位或对)也被证明是一个精细可调的参数,为合理设计具有可预测结构-性质关系的定制bTAA发射器开辟了新的机会。
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引用次数: 0
Synthesis of the Pentasaccharide Repeating Unit Corresponding to the Cell Wall O-Polysaccharide of Salmonella riogrande O:40 (Group R) Strain riogrande沙门氏菌O:40 (R组)细胞壁O-多糖对应的五糖重复单元的合成
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-02-01 DOI: 10.1002/ejoc.202501215
Saikat Dogra, Anup Kumar Misra
Synthesis of a pentasaccharide corresponding to the repeating unit of the cell wall O-polysaccharide of Salmonella riogrande O:40 has been achieved in very good yield. During the process of synthesis, construction of the α-D-galactosamine moiety was achieved by using 2-azido-2-deoxy-D-galactosamine thioglycoside donor in ether-based reaction solvent. Construction of the β-mannosidic linkage in the pentasaccharide was achieved using remotely placed picoloyl group influenced H-bond mediated aglycone delivery. All glycosylation steps were high yielding with satisfactory stereochemistry at the newly formed glycosidic linkages. Azido group was directly converted into acetamido group by the treatment with thioacetic acid and triethylsilane was used as the source of hydrogen in a catalytic transfer hydrogenation condition.
合成了一种与沙门氏菌O-多糖O:40细胞壁重复单元相对应的五糖,产率很高。在合成过程中,采用2-叠氮-2-脱氧-d -半乳糖胺硫苷给体在醚基反应溶剂中构建α- d -半乳糖胺部分。利用远程放置的picoloyl基影响氢键介导的苷元传递,在五糖中构建了β-甘露糖苷键。所有糖基化步骤产率高,新形成的糖苷键具有令人满意的立体化学性质。在催化转移加氢条件下,以三乙基硅烷为氢源,经硫乙酸处理,叠氮基直接转化为乙酰胺基。
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引用次数: 0
Photochemical Amination of Thioethers Under Biphasic Flow Conditions 双相流条件下硫醚的光化学胺化
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-01-30 DOI: 10.1002/ejoc.202501165
Calvine Lai, Hélène Lebel
A practical, continuous flow, biphasic photochemical amination of thioethers, employing N ‐mesyloxycarbamates as nitrene precursors, is reported. Using UVA irradiation at 365 nm and Fe(acac) 3 as a catalyst, the reaction efficiently converts aromatic and aliphatic thioethers into Troc‐protected sulfilimines in high yields. The biphasic ethyl acetate/water system plays a critical role in preventing clogging of the reactor by dissolving the mesylate byproduct.
报道了一种实用的、连续流动的、双相光化学胺化硫醚,采用N‐甲氧氨基甲酸酯作为亚硝基前体。在365nm的UVA照射下,以Fe(acac) 3为催化剂,将芳香族和脂肪族硫醚高效转化为Troc保护的亚亚胺,收率高。双相乙酸乙酯/水体系通过溶解甲磺酸副产物在防止反应器堵塞方面起着关键作用。
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引用次数: 0
TBAF‐Catalyzed Conversion of Carbamates Into Unsymmetrical Ureas TBAF催化氨基甲酸酯转化为不对称脲
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-01-30 DOI: 10.1002/ejoc.202500761
Ajay Singh, Suruchi Ojha, Manish Yadav, Anuj Mishra, Manjinder Singh Gill
This study investigates the synthesis of unsymmetrical ureas involving tetra‐ n ‐butylammonium fluoride (TBAF) catalyzed in situ generation of isocyanate of N ‐alkyl/aryl O ‐phenyl carbamates at room temperature that subsequently reacts with alkyl/aromatic amines to yield unsymmetrical urea with moderate to excellent yields including gram scale synthesis of celiprolol intermediate. The process of employing TBAF an organocatalyst, thus, eliminates the use of hazardous reagents, hence making the process sustainable, cost‐effective, and additive free.
本研究研究了四n - n -丁基氟化铵(TBAF)在室温下原位催化n -烷基/芳基O -苯基氨基甲酸酯异氰酸酯合成不对称尿素的方法,该方法随后与烷基/芳香胺反应生成不对称尿素,产率中等至优异,包括克级合成塞利洛尔中间体。因此,使用TBAF有机催化剂的过程消除了危险试剂的使用,从而使该过程可持续,成本效益高,无添加剂。
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引用次数: 0
T-Shaped 8-Aryl(ethynyl)-Substituted Psoralens With Tunable Charge-Transfer Absorption 可调电荷转移吸收的t形8-芳基(乙基)取代补骨脂素
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-01-30 DOI: 10.1002/ejoc.202501175
Lena T. Leusch, Thomas J. J. Müller
Two series of novel T-shaped 8-substituted psoralen derivatives bearing (hetero)aryl and arylethynyl substituents were synthesized via Suzuki and Sonogashira coupling starting from 8-methoxypsoralen (8-MOP). Predominantly, electron-donating substituents such as anisyl and phenothiazine were introduced at the 8-position of the psoralen for increasing the electron density in comparison to 8-MOP. Photophysical properties were studied by absorption and emission spectroscopy in solution and in the solid state. Increasing the donor strength of the substituent causes a bathochromic shift of both absorption and emission maxima. The absorption behavior can be correlated with Hammett substituent parameters of remote substituents at the p-aryl moieties that are directly or by ethynyl spacing positioned at the 8-position of psoralen. In most cases, fluorescence in the solid state is more pronounced than in solution. One derivative also displays significant aggregation-induced emission. For two amino-substituted psoralen derivatives, positive emission solvatochromism was observed and associated with a considerable change of dipole moment upon photonic excitation according to Lippert–Mataga analysis. Furthermore, the pKa value of the T-shaped dimethylaminophenyl psoralen derivative was determined from absorption spectra. In addition, emission quenching is caused by protonation on the nitrogen atom. TD-DFT (time-dependent density functional theory) calculations are in good agreement with experimental data and rationalize the electronic structure.
以8-甲氧基补骨脂素(8-MOP)为原料,通过Suzuki和Sonogashira偶联法合成了两个新型的8-取代补骨脂素t型衍生物,分别含有(杂)芳基和芳基乙基取代基。与8-MOP相比,在补骨脂素的8位上主要引入了给电子取代基,如茴香基和吩噻嗪,以增加电子密度。利用吸收光谱和发射光谱研究了其在溶液和固体状态下的光物理性质。增加取代基的施主强度会引起吸收和发射最大值的色移。吸附行为可与补骨脂素8位上的对芳基基或乙基间距上的远端取代基的Hammett取代参数相关。在大多数情况下,荧光在固态比在溶液中更明显。一种衍生物也表现出明显的聚集诱导发射。根据Lippert-Mataga分析,对于两种氨基取代的补骨脂素衍生物,观察到正发射溶剂变色现象,并与光子激发时偶极矩的相当大的变化有关。利用吸收光谱测定了t型二甲基氨基苯基补骨脂素衍生物的pKa值。此外,发射猝灭是由氮原子的质子化引起的。TD-DFT(时变密度泛函理论)计算结果与实验数据吻合较好,使电子结构合理化。
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引用次数: 0
Photoinduced Silver(I)‐Mediated Direct Alkoxycarbonylation of Quinoxalin‐2(1 H )‐ones With Alkyloxalyl Chlorides 光诱导银(I)‐介导的喹啉- 2(1 H)‐与烷基氧基氯直接烷氧羰基化
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-01-28 DOI: 10.1002/ejoc.202501140
Yu‐Tong Zhou, Shi‐Ya He, Wu Liang, Fang Liu, Xin‐Ran Sun, Shao‐Qun Cai, Zhi Yang, Jun‐Fei Zhao, Shi‐Cui Fang, Bin Pan, Fei Du
A silver‐ and light‐mediated radical alkoxycarbonylation of quinoxalin‐2(1 H )‐ones has been developed. This direct esterification protocol provides efficient access to quinoxaline‐3‐carboxylates. The operationally simple reaction features good functional group compatibility, and mild conditions. Notably, the successful late‐stage functionalization of complex molecules demonstrates significant synthetic utility for modifying biologically active natural products.
喹啉- 2(1 H) -酮的银和光介导的自由基烷氧羰基化已经被开发出来。这种直接酯化方案提供了喹诺啉‐3‐羧酸酯的有效途径。该反应操作简单,官能团相容性好,反应条件温和。值得注意的是,复杂分子的成功后期功能化证明了对生物活性天然产物进行修饰的重要合成效用。
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引用次数: 0
Telescopic Synthesis of Triazol‐4‐yl Modified Phenylalanine Conjugates and Peptide Modification Using a Sonogashira Domino Strategy at Room Temperature 室温下三氮唑- 4 -基修饰苯丙氨酸缀合物的缩合合成及Sonogashira多米诺效应多肽修饰
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-01-28 DOI: 10.1002/ejoc.202501066
Karuna Thakare, Aman Singh Barahdia, Rahul Jain
We report a telescopic two‐step synthetic strategy for efficiently constructing [1 H ]‐1,2,3‐triazol‐4‐yl modified phenylalanine conjugates. The method combines Sonogashira coupling and a one‐pot domino reaction involving desilylation, azidation, and click chemistry. This protocol enhances the potential for peptide modification and facilitates the synthesis of polyazide derivatives that can be suitable for dendrimeric cores. This reaction yields good results and provides a scalable route, successfully accommodating a wide range of aromatic and heteroaromatic methyl bromides, while achieving excellent chiral integrity and 100% 1,4‐regioselectivity. We also explored the application of a 1,4‐disubstituted [1 H ]‐1,2,3‐triazol‐4‐yl phenylalanine conjugate as a directing group for C(sp 2 )‐H di‐halogenation.
我们报道了一种可伸缩的两步合成策略,可以有效地构建[1 H]‐1,2,3‐三唑‐4‐基修饰的苯丙氨酸偶联物。该方法结合了Sonogashira偶联和涉及脱硅、叠氮化和点击化学的一锅多米诺反应。该方案提高了多肽修饰的潜力,并促进了多叠氮衍生物的合成,可以适用于树突核。该反应产生了良好的结果,并提供了一个可扩展的途径,成功地容纳了广泛的芳香族和杂芳香族甲基溴,同时实现了优异的手性完整性和100%的1,4‐区域选择性。我们还探索了1,4 -二取代[1 H] - 1,2,3 -三唑- 4 -基苯丙氨酸缀合物作为C(sp 2) - H二卤化的导向基团的应用。
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引用次数: 0
Biomass‐Based H 2 S Scavengers: Michael Acceptors 基于生物质的h2s清除剂:迈克尔受体
IF 2.8 3区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2026-01-27 DOI: 10.1002/ejoc.202501122
Xifu Liang, Victor Friis, Karolina Agata Szlek, Asger Munk Koue, Jesper Bendix, Lars Skjolding, Sergey Kucheryavskiy, Marco Maschietti, Christian Marcus Pedersen
Michael acceptors derived from biomass resources, such as carbohydrates, have been synthesized and their H 2 S scavenging properties studied. The most promising candidates were compared with the commercial H 2 S scavenger MEA‐triazine by studying the aqueous phase scavenging reactions using in situ Raman spectroscopy and the gas–liquid reactions were evaluated in a flow setup. Based on cost and scavenging efficiency considerations, the industrially most promising candidates were submitted to ecotoxicity studies. We have found three families of Michael acceptors, which are readily available and can be tailor‐made to serve as sulfide scavengers under different conditions.
合成了来源于碳水化合物等生物质资源的Michael受体,并对其清除h2s的性能进行了研究。通过原位拉曼光谱研究水相清除反应,比较了最有希望的候选物与商业h2s清除剂MEA -三嗪,并在流动装置中评估了气液反应。基于成本和清除效率的考虑,工业上最有希望的候选材料被提交给生态毒性研究。我们发现了三个Michael受体家族,它们很容易获得,可以在不同条件下作为硫化物清除剂。
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引用次数: 0
期刊
European Journal of Organic Chemistry
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