Tetrahedron最新文献

英文中文

Tuning the photophysical and NLO properties of β-diketonates derived from coumarin-triphenylamine-chalcones: Effect of the BF2 group 调谐香豆素-三苯胺-查耳酮衍生的 β-二酮酸酯的光物理和 NLO 特性：BF2 基团的影响

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-26 DOI: 10.1016/j.tet.2024.134338

Edgard Fabián Blanco-Acuña , Iván Alessandro Texon-García , Luis Antonio Vázquez-López , Alfredo Pérez-Gamboa , Héctor García-Ortega

Herein the synthesis of three difluoroboron β-diketonate complexes (7a-c) and one chalcone (7d) with coumarin and triphenylamine fragments is described. The effect of the inclusion of the difluoroboron (BF₂) group and a phenyl linker on the photophysical properties, intramolecular charge transfer (ICT) and nonlinear optical (NLO) properties was studied. These dyes exhibited excellent ICT properties due to their A-π-D and D-π-A-π-D type push-pull configuration. Thus, all compounds presented a strong solvatochromism, given the absorption and emission maxima shifted to red because of the increase in the polarity of the medium. In addition to this, 7a-d showed the formation of a twisted intramolecular charge transfer (TICT) state, which quenched fluorescence in polar solvents. Compounds 7a, 7b and 7d exhibited aggregation-induced emission (AIE) in MeCN/H₂O mixtures, while 7c did not have this behavior. In addition, all compounds showed emission in the solid state. Using DFT and TD-DFT calculations, the molecular geometries of the ground state S₀ and the first excited state S₁ were elucidated, which confirmed the formation of a TICT state. Furthermore, the theoretical and experimental absorption electronic transitions were correlated by testing different functionals: B3LYP, CAM-B3LYP, PBE0, wB97XD, HSEH1PBE and M062X. Frontier molecular orbitals (FOMs) and molecular electrostatic potentials (MEPs) supported the ICT from the donor to the acceptor group. The global reactivity descriptors were studied and the NLO properties were predicted by calculating first (β_tot) and second-order (γ_ave) hyperpolarizabilities, revealing that 7a-d would present promising NLO behavior.

本文介绍了三种二氟硼β-二酮配合物（7a-c）和一种含有香豆素和三苯胺片段的查尔酮（7d）的合成。研究了加入二氟硼（BF2）基团和苯基连接剂对光物理特性、分子内电荷转移（ICT）和非线性光学（NLO）特性的影响。由于这些染料具有 A-π-D 和 D-π-A-π-D 型推拉构型，因此表现出优异的 ICT 特性。因此，由于介质极性的增加，吸收和发射的最大值向红色移动，所有化合物都呈现出强烈的溶解变色现象。此外，7a-d 还形成了分子内电荷转移（TICT）扭曲态，在极性溶剂中淬灭了荧光。化合物 7a、7b 和 7d 在 MeCN/H2O 混合物中显示出聚集诱导发射（AIE），而 7c 则没有这种行为。此外，所有化合物在固态下都显示出发射。通过 DFT 和 TD-DFT 计算，阐明了基态 S0 和第一激发态 S1 的分子几何结构，证实了 TICT 态的形成。此外，通过测试不同的函数，对理论和实验吸收电子跃迁进行了相关分析：B3LYP、CAM-B3LYP、PBE0、wB97XD、HSEH1PBE 和 M062X。前沿分子轨道（FOMs）和分子静电位（MEPs）支持从供体基团到受体基团的信息和通信技术。通过计算一阶（βtot）和二阶（γave）超极化率，研究了全局反应性描述符并预测了 NLO 特性，结果表明 7a-d 具有良好的 NLO 行为。

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引用次数: 0

DFT calculations of properties of CF3-carbocations of the thiophene series as key intermediates in the synthesis of novel CF3-thiophenes 噻吩系列 CF3-配位物作为合成新型 CF3-噻吩的关键中间体的性质的 DFT 计算

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-25 DOI: 10.1016/j.tet.2024.134321

Olesya V. Khoroshilova , Irina A. Boyarskaya , Aleksander V. Vasilyev

Trimethylsilyl ethers of thiophen-2-yl-(trifluoromethyl)methanols undergo multichannel electrophilic transformations under the action of Brønsted superacid acid CF₃SO₃H to form a wide range of CF₃-substituted thiophene structures. The key cationic intermediates of these transformations are CF₃-carbocations. Electronic and orbital characteristics, global electrophilicity indices, and thermodynamic characteristics of these key intermediates have been calculated with a use of the density functional theory (DFT). Experimental data on the reactivity of intermediate cationic species have been explained on the basis of the results of quantum chemical calculations. It has been shown that reactions of the cations with aromatic nucleophiles are mainly ruled by orbital control.

噻吩-2-基-(三氟甲基)甲醇的三甲基硅醚在布氏超酸性酸 CF3SO3H 的作用下发生多通道亲电转化，形成多种 CF3 取代的噻吩结构。这些转化的关键阳离子中间体是 CF3-配位体。利用密度泛函理论（DFT）计算了这些关键中间产物的电子和轨道特征、全局亲电指数以及热力学特征。量子化学计算的结果解释了中间阳离子物种反应性的实验数据。结果表明，阳离子与芳香族亲核物的反应主要受轨道控制。

引用次数: 0

Unprecedented synthesis of indole-linked tetra-substituted alkenes by catalyst-free domino reaction 通过无催化剂多米诺反应前所未有地合成吲哚连接的四取代烯烃

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-24 DOI: 10.1016/j.tet.2024.134327

Darakshan, Ujjain Chaurasia, Aatka Mehar, Tasneem Parvin

Herein, we report a simple, efficient catalyst-free green domino reaction of indole, arylglyoxal, and cyclic 1,3-dicarbonyls such as barbituric acid derivatives/dimedone at 100 °C in dimethylformamide medium in open air condition. In this reaction, one C–C and one CC bonds have been formed in one-pot without using any additive or metal based reagent. Considering the presence of indole, benzoyl and cyclic 1,3-dicarbonyl moieties in the products, it is expected that they will exhibit interesting medicinal properties. All the synthesized products were characterized by recording FTIR, ¹H NMR, ¹³C NMR, and HRMS. Moreover, a single crystal XRD of compound 4j was recorded to confirm the structure of the product. Operational simplicity, gram-scale synthesis, mild reaction conditions, good yields, and wide substrate scope are the salient features of this methodology.

在此，我们报告了一种简单、高效、无催化剂的绿色多米诺反应，该反应在 100 °C、二甲基甲酰胺介质中露天条件下进行，反应物包括吲哚、芳基乙二醛和环状 1,3-二羰基（如巴比妥酸衍生物/二甲酮）。在该反应中，无需使用任何添加剂或金属试剂，就能在一锅中形成一个 C-C 键和一个 CC 键。考虑到产品中存在吲哚、苯甲酰基和环 1,3-二羰基，预计它们将表现出有趣的药用特性。所有合成产品都通过傅立叶变换红外光谱、1H NMR、13C NMR 和 HRMS 进行了表征。此外，还记录了化合物 4j 的单晶 XRD，以确认产品的结构。该方法操作简单、合成规模为克级、反应条件温和、产率高、底物范围广是其显著特点。

引用次数: 0

Synthesis and investigation of photo-physical properties of fluorescent dyes obtained by the Knoevenagel condensation of mono-, di- or tri-formyl aromatic aldehydes and various CH-acid derivatives 通过单、二或三芳基芳香醛与各种 CH 酸衍生物的 Knoevenagel 缩合获得的荧光染料的合成及其光物理特性研究

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-24 DOI: 10.1016/j.tet.2024.134325

A. Pałasz, P. Goszczycki, D. Cież, A. Błaszków, A. Marchewka, M. Ogos, D. Barczyk

Fluorescent dyes were constructed using the Knoevenagel condensation of the appropriate aldehydes and CH-acid derivatives. Aromatic aldehydes containing one, two or three formyl groups were used as substrates. Cyanoacetamide, ethyl cyanoacetate, benzoylacetonitrile and indan-1,3-dione play the role of CH-acid derivative. The appropriate aldehydes were obtained by the Duff formylation reaction. The dyes synthesis procedure was very simple. The condensation was carried out in water in the presence of NaOH, as the basic catalyst at room temperature, and the dyes were obtained in yields between 58 and 93 %. The work-up procedure was very simple, and the products do not require any further purification. The great advantages of this synthetic procedure are its simplicity, cheapness, compliance with the rules of green chemistry and the fact that it efficiently leads to structurally complex fluorescent dyes. Twenty-three new compounds were obtained, eleven of which exhibited fluorescence in solution and four in the solid state. Taking into account the fluorescence quantum yield and the emission maximum value close to the NIR range, the dye constructed by condensation of indan-1,3-dione and methyl 3,5-diformyl-4-hydroxybenzoate meets the above-mentioned requirements (Φ = 16 %, λ_em = 660 nm) best. The dye with the highest value of Φ = 25 % in solid is a derivative of cyanoacetamide and 3,4,5-trimethoxybenzaldehyde.

荧光染料是利用适当的醛和 CH 酸衍生物的 Knoevenagel 缩合反应制成的。含有一个、两个或三个甲酰基的芳香醛被用作底物。氰乙酰胺、氰乙酸乙酯、苯甲酰乙腈和茚满-1,3-二酮扮演 CH 酸衍生物的角色。通过达夫甲酰化反应可以得到相应的醛。染料的合成过程非常简单。缩合反应在室温下，以 NaOH 为碱性催化剂，在水中进行，染料的收率在 58% 到 93% 之间。加工程序非常简单，产品无需进一步提纯。这种合成方法的最大优点是简单、廉价、符合绿色化学规则，而且能有效地得到结构复杂的荧光染料。我们获得了 23 种新化合物，其中 11 种在溶液中显示荧光，4 种在固态中显示荧光。考虑到荧光量子产率和接近近红外范围的发射最大值，由茚-1,3-二酮和 3,5-二甲酰基-4-羟基苯甲酸甲酯缩合而成的染料最符合上述要求（Φ = 16 %，λem = 660 nm）。固体中 Φ = 25 % 值最高的染料是氰乙酰胺和 3,4,5-三甲氧基苯甲醛的衍生物。

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引用次数: 0

Approach to extended polycyclic aromatic hydrocarbons by benzannulation and intramolecular cyclization; improvement of the reaction conditions by microwave irradiation 通过苯annulation 和分子内环化反应制备扩展的多环芳烃；利用微波辐照改善反应条件

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-24 DOI: 10.1016/j.tet.2024.134332

Rui Umeda, Raiki Nishikawa, Taketo Matsui, Kotaro Takase

The extended π-conjugated compounds 1–8 were synthesized by the benzannulation of the corresponding alkyne derivatives followed by Pd-catalyzed intramolecular cyclization. For the Pd-catalyzed intramolecular cyclization, microwave irradiation reduced the amount of the Pd catalyst and the reaction time. Moreover, this protocol can be achieved to prepare the extended and twisted π-conjugated molecule 19, having anthracene, helicene, and picene skeletons.

扩展的π-共轭化合物 1-8 是通过相应炔衍生物的苯并环化和钯催化的分子内环化合成的。在钯催化的分子内环化反应中，微波辐照减少了钯催化剂的用量和反应时间。此外，这种方法还可以制备出具有蒽、螺旋烯和皮烯骨架的扩展和扭曲的π-共轭分子 19。

引用次数: 0

Paradigm shift in medicinal products synthesis: Continuous flow technology 药用产品合成的范式转变：连续流技术

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-24 DOI: 10.1016/j.tet.2024.134333

Bryce L. Koeberg , Mellisa B. Sagandira , Cloudius R. Sagandira , Paul Watts

About 80 % of the population in developing economies such as Africa use traditional medicines for healthcare. Traditional medicines from diverse cultures have been recognized for their efficacy and cost-effectiveness in improving health in developing economies. Access to synthetic natural products is typically associated with challenges such as lengthy synthetic routes, large environmental footprint, complex chemical architecture and time-consuming and purification processes. Continuous flow technology has emerged as a potent and enabling tool in the synthesis of complex natural products because of its efficiency and environmentally benign nature. Herein, we review advances in continuous flow synthesis of diverse natural products with biological activity to demonstrate the impact and potential of the technology in overcoming challenges faced in natural products synthesis. Consequently, this allows for easy and efficient access to atypical or structurally complex natural products. Overall, this article highlights the transformative impact of continuous flow technology on the bioactive natural products synthesis and offer a useful reference tool for chemists interested in the synthesis of these compounds.

在非洲等发展中经济体，约 80% 的人口使用传统药物进行保健。来自不同文化的传统药物在改善发展中经济体的健康状况方面的功效和成本效益已得到认可。获取合成天然产品通常会面临诸多挑战，如合成路线长、环境影响大、化学结构复杂以及纯化过程耗时等。连续流技术因其高效和对环境无害的特性，已成为合成复杂天然产物的有力工具。在此，我们回顾了具有生物活性的多种天然产物的连续流合成进展，以展示该技术在克服天然产物合成所面临的挑战方面的影响和潜力。因此，这使得非典型或结构复杂的天然产品的获得变得简单而高效。总之，本文强调了连续流技术对生物活性天然产物合成的变革性影响，并为对合成这些化合物感兴趣的化学家提供了有用的参考工具。

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引用次数: 0

Regioselective C(sp2)-H nitrosation and nitration of (Hetero)arenes with Fe(NO3)3·9H2O as promoter, nitroso and nitro source 以Fe(NO3)3-9H2O为促进剂、亚硝基和硝基源的（异）烷的区域选择性C(sp2)-H亚硝化和硝化反应

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-23 DOI: 10.1016/j.tet.2024.134329

Ailong Shao, Yuanyuan Li, Min Dong, Yuhang Wang, Rongjing Zhao, Jun Zhang, Shuisheng Chen, Hai Wu

A regioselective C(sp²)-H nitrosation and nitration protocol has been successfully developed for the modification of various undirected bioactive molecules by using the economical and nontoxic Fe(NO₃)₃^.9H₂O as nitroso/nitro source. This method is conducted under acid-free and ease of handling conditions and is featured with good regioselectivity as well as a broad substrate scope (38 examples; yields up to 90 %). This reaction could be conducted on a gram scale with good efficiency, demonstrating high utility for the synthesis and modification of drug and material molecules. Detailed mechanistic studies indicate that the formation of the nitroso or nitro products might be proceeded via the radical cross coupling of aryl radical cation intermediates with nitroso or nitro radical.

利用经济、无毒的 Fe(NO3)3.9H2O 作为亚硝基/硝基源，成功开发了一种具有区域选择性的 C(sp2)-H 亚硝基化和硝化方法，用于修饰各种非定向生物活性分子。该方法在无酸和易于操作的条件下进行，具有良好的区域选择性和广泛的底物范围（38 个实例；收率高达 90%）。该反应可在克级规模上进行，且效率很高，在药物和材料分子的合成和改性方面具有很高的实用性。详细的机理研究表明，亚硝基或硝基产物的形成可能是通过芳基自由基阳离子中间体与亚硝基或硝基自由基的自由基交叉偶联进行的。

引用次数: 0

Oxazaborolidine catalyzed asymmetric 1,4-addition of diarylphosphine oxides to α,β-unsaturated N-acylindoles and N-acylpyrroles 噁唑硼烷催化二芳基膦氧化物与 α、β-不饱和 N-酰基吲哚和 N-酰基吡咯的不对称 1,4-加成反应

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-23 DOI: 10.1016/j.tet.2024.134331

Jinyi Qian, Wendi Shao, Qi Gao, Jiuling Li, Baomin Fan, Yafei Guo

The enantioselective 1,4-addition of diarylphosphine oxides to α,β-unsaturated N-acylindoles and N-acylpyrroles catalyzed by a commercial chiral oxazaborolidine is reported. This methodology tolerates a variety of substrates and diarylphosphine oxides, leading to high yields and enantioselectivities. Importantly, the resulting chiral products exhibit excellent transformation abilities to form corresponding acids, amides, and esters with high potential applications in the synthesis of chiral phosphine ligands.

报告了在一种商用手性噁唑硼烷催化下，二芳基膦氧化物与 α、β-不饱和 N-酰基吲哚和 N-酰基吡咯的 1,4-对映体选择性加成。该方法可耐受多种底物和二元膦氧化物，从而获得高产率和高对映选择性。重要的是，所得到的手性产物具有极佳的转化能力，可以形成相应的酸、酰胺和酯，在手性膦配体的合成中具有极高的应用潜力。

引用次数: 0

Dithiolation of [60]fullerene with aliphatic primary thiols initiated by n-butylamine via aerobic oxidation reaction 正丁胺通过有氧氧化反应引发[60]富勒烯与脂肪族伯硫醇的二硫化反应

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-22 DOI: 10.1016/j.tet.2024.134313

Sheng-Li Wu , Yu-Bo Li , Song-Xiao Yu , Peiwen Lv , Jintao Guan , Yi Wang , Zong-Jun Li

A facile aerobic oxidation reaction of [60]fullerene with aliphatic primary thiols initiated by n-butylamine was studied. Interestingly, the reaction yielded liquid mixtures upon solvent evaporation, contrary to the typical formation of solid mixtures. The reaction products were purified using HPLC to isolate the fullerene dithiol epoxide compound (2), which was extensively characterized by ¹H NMR, ¹³C NMR, HRMS, and UV–Vis spectra. Plausible reaction mechanisms leading to the formation of the observed products were proposed. Computational simulations and control experiment were conducted to elucidate the proposed reaction mechanisms. The electrochemical behavior of 1,2-O-4,15-(n-C₅H₁₁S)₂C₆₀ (2) was investigated, revealing its instability upon gradual reduction.

研究了由正丁胺引发的[60]富勒烯与脂肪族伯硫醇的简易有氧氧化反应。有趣的是，该反应在溶剂蒸发后会产生液态混合物，而不是典型的固态混合物。通过 HPLC 对反应产物进行纯化，分离出富勒烯二硫环氧化物化合物 (2)，并通过 1H NMR、13C NMR、HRMS 和 UV-Vis 光谱对其进行了广泛表征。研究人员提出了形成所观察到的产物的合理反应机制。为阐明所提出的反应机制，进行了计算模拟和对照实验。研究了 1,2-O-4,15-(n-C5H11S)2C60 (2) 的电化学行为，揭示了其在逐渐还原时的不稳定性。

引用次数: 0

Amide synthesis from DDQ-mediated electrochemical Beckmann rearrangement 通过 DDQ 介导的电化学贝克曼重排合成酰胺

IF 2.1 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2024-10-22 DOI: 10.1016/j.tet.2024.134324

Ren-Yu Tian , Mohammad Sanayi Haqmal , Yu-Ting Bao , Shi-Yao Liu , Guang-Ying Chen , Li Tang

Beckmann rearrangement, a classical reaction of introducing nitrogen to carbon skeleton compounds for amide synthesis, is widely used in academia and industry. Herein, an electrochemical Beckmann rearrangement is reported, utilizing 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as a mediator to prevent the over-electro-oxidation of products, which could afford amide in excellent yield.

贝克曼重排是将氮引入碳骨架化合物进行酰胺合成的经典反应，在学术界和工业界得到广泛应用。本文报道了一种电化学贝克曼重排反应，利用 2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）作为介质防止产物过度电氧化，从而以优异的收率获得酰胺。

引用次数: 0

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