Tetrahedron最新文献

英文中文

Synthesis and antibacterial evaluation of a unique amide library based on the marine natural product 3,5-dibromo-4-methoxybenzoic acid 基于海洋天然产物3,5-二溴-4-甲氧基苯甲酸的独特酰胺库的合成及抗菌评价

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-17 DOI: 10.1016/j.tet.2025.135104

Sasha Hayes , Jonathan M. White , Bernd H.A. Rehm , Rohan A. Davis

Chemical investigations of the Australian marine sponge Ianthella basta resulted in the isolation of six known secondary metabolites, which included bastadins 4 (1), 5, (2) 8 (3) and 13 (4), 3,5-dibromo-4-methoxybenzeneacetic acid (5) and 3,5-dibromo-4-methoxybenzoic acid (6). The screening of these metabolites for inhibitory activity towards Pseudomonas aeruginosa (strain PAO1) for planktonic cell growth and biofilm formation identified metabolite 6 as a biofilm inhibitor. Based on these data a 13 membered semisynthetic amide library was generated using metabolite 6 as a scaffold for medicinal chemistry studies. Whilst none of the new semisynthetic compounds increased inhibitory activity towards PAO1 compared to the original scaffold, additional screening of the natural and semisynthetic library against the clinically relevant strain PDO300 showed that some of the secondary metabolites inhibited planktonic growth and biofilm formation. Furthermore, all semisynthetic compounds displayed increased inhibitory activity of planktonic growth with N,N'-((butane-1,4-diylbis(azanediyl))bis(propane-3,1-diyl))bis(3,5-dibromo-4-methoxybenzamide) (19) displaying 46 % planktonic inhibition and 3,5-dibromo-N-(4-fluorophenethyl)-4-methoxybenzamide (14) inhibiting biofilm formation by 21 % at 50 μM. All semisynthetic derivatives were obtained in yields ranging from 3 % to 79 %, and in purities >95 %. All new natural product derivatives were fully characterized following 1D/2D NMR, LRESIMS and HRESIMS data analysis; two semisynthetic compounds were crystalline, which enabled X-ray diffraction studies. The new chemistry and biology reported here indicate that the bastadin and 3,5-dibromo-4-methoxybenzoic acid motifs warrant further investigation against P. aeruginosa.

对澳大利亚海绵Ianthella basta进行化学研究，分离出6种已知的次生代谢产物，包括bastadins 4(1)、5(2)、8(3)和13(4),3,5-二溴-4-甲氧基苯乙酸(5)和3,5-二溴-4-甲氧基苯甲酸(6)。筛选这些代谢物对铜绿假单胞菌（菌株PAO1）浮游细胞生长和生物膜形成的抑制活性，鉴定代谢物6为生物膜抑制剂。基于这些数据，以代谢物6为骨架，构建了一个13元半合成酰胺文库，用于药物化学研究。虽然与原始支架相比，新的半合成化合物没有增加对PAO1的抑制活性，但对临床相关菌株PDO300的天然和半合成文库的额外筛选表明，一些次级代谢物抑制了浮游生物的生长和生物膜的形成。此外，所有半合成化合物均显示出对浮游生物生长的抑制活性，其中N，N'-（（丁烷-1,4-二基双（氮二基）））-（丙烷-3,1-二基）)-（3,5-二溴-4-甲氧基苯甲酰胺）（19）对浮游生物的抑制作用为46%，3,5-二溴-N-（4-氟苯基）-4-甲氧基苯甲酰胺（14）在50 μM下对生物膜形成的抑制作用为21%。所有半合成衍生物的产率从3%到79%不等，纯度为95%。所有新的天然产物衍生物均通过1D/2D NMR、LRESIMS和HRESIMS数据分析进行了全面表征；两种半合成化合物是结晶的，这使得x射线衍射研究成为可能。新的化学和生物学报道表明，巴斯丁和3,5-二溴-4-甲氧基苯甲酸基序值得进一步研究P. aeruginosa。

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引用次数: 0

Diels-Alder reaction: A versatile synthetic tool for the synthesis of terpenoids and alkaloids: A review Diels-Alder反应：一种合成萜类和生物碱的通用合成工具

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-17 DOI: 10.1016/j.tet.2025.135101

Muhammad Ikram , Asim Mansha , Samreen Gul Khan , Ameer Fawad Zahoor , Muhammad Naveed Anjum , Kulsoom Ghulam Ali , Freeha Hafeez , Aijaz Rasool Chaudhry , Ahmad Irfan , Muhammad Abbas

Diels-Alder reaction is a powerful transformation in organic synthesis due to its great potency to generate 6-membered ring system with multiple stereogenic centers in a concerted manner. This pericyclic reaction has been utilized for the construction of numerous complex scaffolds with highly intricate patterns. Herein, this widely studied topic in chemistry has been discussed in detail with its recent applications towards terpenoids and alkaloids, reported since 2020. Different modifications in Diels-Alder substrates, Lewis acids and organo-metallic catalysts further expand the utility of this reaction. The effect of substitution pattern on Diels-Alder substrates and other structural motifs has also been highlighted in this review which shows significant influence of the stereo- and regio-chemistry of Diels-Alder reaction in chasing the target molecule.

Diels-Alder反应是有机合成中一个强有力的转变，因为它能以协调一致的方式生成具有多个立体中心的6元环体系。这种周环反应已被用于构建许多具有高度复杂图案的复杂支架。本文详细讨论了这一广泛研究的化学主题，以及其自2020年以来在萜类和生物碱方面的最新应用。Diels-Alder底物、Lewis酸和有机金属催化剂的不同修饰进一步扩大了该反应的用途。本文还重点介绍了取代模式对Diels-Alder底物和其他结构基序的影响，表明Diels-Alder反应的立体化学和区域化学对追逐靶分子有重要影响。

引用次数: 0

Advances in pyrazolone functionalization: A review since 2020 吡唑酮功能化研究进展：2020年以来综述

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-17 DOI: 10.1016/j.tet.2025.135103

Mao-Lin Liao , Peng-Peng Liu , Chang-Liang Tan , Ping-Gui Li , Liang-Hua Zou

Pyrazolones are a class of nitrogen-containing heterocyclic compounds of great value in the fields of synthetic chemistry and medicinal chemistry. This review comprehensively summarizes the iconic research progress of pyrazolone functionalization reactions since 2020, including monosubstitution at the 4-position, 3,4,6-position annulation for constructing fused ring systems, 4-position disubstitution for spirocycle construction, and heterocycle construction involving the N–N bond. Through the use of novel catalysts, unique reaction conditions, and innovative reaction pathways, these reactions exhibit high selectivity, good substrate adaptability, and excellent atom economy. These advancements not only enrich the synthetic methods of pyrazolone derivatives but also provide important references for the development of novel bioactive molecules and functional materials, strongly promoting the development of related fields such as organic synthesis and drug research and development.

吡唑酮类化合物是一类含氮杂环化合物，在合成化学和药物化学领域具有重要的应用价值。本文综述了自2020年以来吡唑酮功能化反应的标志性研究进展，包括4位、3位、4位、6位环的单取代构建融合环体系，4位二取代构建螺旋环，以及涉及N-N键的杂环构建。通过使用新颖的催化剂、独特的反应条件和创新的反应途径，这些反应具有高选择性、良好的底物适应性和优异的原子经济性。这些进展不仅丰富了吡唑酮衍生物的合成方法，而且为新型生物活性分子和功能材料的开发提供了重要参考，有力地促进了有机合成和药物研发等相关领域的发展。

引用次数: 0

Gram-scale reduction of esters to alcohols using AlCl3/NaBH4 revisited: Solvent effect, scope, and limitations 用AlCl3/NaBH4还原克级酯为醇：溶剂效应、范围和限制

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-15 DOI: 10.1016/j.tet.2025.135102

Hai-yang Chen , Eman Fayad , Dalal Nasser Binjawhar , Hua-Li Qin

Herein, we revisit the reduction of esters to primary alcohols using sodium borohydride and aluminum chloride. Solvent selection proved critical. An improved, more convenient procedure has been developed by replacing conventional diglyme with DME (1,2-dimethoxyethane). Mild reaction conditions, good functional group compatibility, gram-scale reaction, and operational simplicity demonstrate the power of this protocol.

在这里，我们重新审视用硼氢化钠和氯化铝还原酯为伯醇。溶剂的选择至关重要。用二甲醚（1,2-二甲氧基乙烷）代替传统的二lyme，开发了一种改进的、更方便的方法。温和的反应条件，良好的官能团相容性，克级反应和操作简单证明了该方案的力量。

引用次数: 0

Synthesis of symmetric aryl sulfides mediated by xanthates: Based on the EDA complex strategy 黄原酸介导对称芳基硫化物的合成：基于EDA配合物策略

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-14 DOI: 10.1016/j.tet.2025.135105

Lisha Wu, Xue Li, DongXiang Yan, Kun Cao, Jiahong Li

An efficient method for symmetric aryl sulfides synthesis is reported. Using low-cost, readily available potassium xanthogenate as sulfur source, it reacts with aryl bromides under light, possibly via two EDA interactions. Potassium xanthogenate acts as electron donor in the first EDA complex and generates key thiophenolate anion. It accesses hard-to-obtain electron-deficient products, tolerates diverse functional groups, and opens new avenues for diaryl sulfides.

报道了一种合成对称芳基硫化物的有效方法。它使用低成本、容易获得的黄原酸钾作为硫源，在光照下与芳基溴发生反应，可能通过两种EDA相互作用。黄原酸钾作为第一个EDA复合物的电子供体，生成关键的硫酚酸阴离子。它获得难以获得的缺电子产物，耐受多种官能团，并为二芳基硫化物开辟了新的途径。

引用次数: 0

Cerium(IV)-mediated nitrooxylation-phosphorylation of α-(trifluoromethyl)styrenes with H-phosphonates and H-phosphine oxides 铈（IV）介导的α-（三氟甲基）苯乙烯与h -膦酸盐和h -膦氧化物的硝基氧化磷酸化反应

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-14 DOI: 10.1016/j.tet.2025.135093

Xuxue Zhang , Jiekun Zhu , Junfeng Teng , Chao Zhou , Hao Xu , Xiaolu Yin , Chenxi Li , Xiaoyi Jiang , Song Cao

An efficient CAN-mediated nitrooxylation-phosphorylation of α-(trifluoromethyl)styrenes with H-phosphonates and H-phosphine oxides was described. This novel difunctionalization reaction could enable the rapid incorporation of nitrooxy group and phosphoryl group into α-(trifluoromethyl)styrene in one step, affording the β-nitrooxy-β-trifluoromethyl-phosphonates and β-nitrooxy-β-trifluoromethyl-phosphine oxides in moderate to good yields.

描述了一种高效的can介导的α-（三氟甲基）苯乙烯与h -膦酸盐和h -膦氧化物的硝基氧化磷酸化反应。这种新型的双官能化反应可使硝基和磷基在一步内快速结合到α-（三氟甲基）苯乙烯中，从而得到中高收率的β-硝基氧基-β-三氟甲基膦酸盐和β-硝基氧基-β-三氟甲基膦氧化物。

引用次数: 0

Phosphine-catalyzed [4 + 2] cycloaddition of benzofuran-derived azadienes and conjugated dienes: Synthesis of 1,2,3,4-tetrahydrobenzofuro[3,2-b]pyridines 膦催化苯并呋喃衍生的氮杂烯和共轭二烯的[4 + 2]环加成：1,2,3,4-四氢苯并呋喃[3,2-b]吡啶的合成

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-14 DOI: 10.1016/j.tet.2025.135100

Shenao Qu , Yue Wang , Er-Qing Li

In this work, we report the phosphine-catalyzed [4 + 2] cycloaddition reaction between benzofuran-derived azadienes and conjugated dienes. This method provides an efficient approach for constructing benzofuran-fused nitrogen-containing heterocyclic skeletons. The reaction features unique regioselectivity, good yields, excellent diastereoselectivity and broad substrate scope. Moreover, the potential synthetic utility of this strategy is demonstrated through gram-scale experiment and subsequent synthetic transformation.

在这项工作中，我们报道了膦催化的苯并呋喃衍生的偶氮二烯与共轭二烯之间的[4 + 2]环加成反应。该方法为构建含氮杂环骨架提供了一种有效的方法。该反应具有区域选择性好、产率高、非对映选择性好、底物范围广等特点。此外，通过克尺度实验和随后的合成转化，证明了该策略的潜在综合效用。

引用次数: 0

Synthesis of 2,3-dihydrothiazole-5-carboxylates via a domino reaction of tetralone-derived β-ketothioamides with nitroallylic acetates 四酮衍生β-酮硫胺与硝酸基乙酸酯多米诺反应合成2,3-二氢噻唑-5-羧酸盐

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-13 DOI: 10.1016/j.tet.2025.135098

Gang Wang , Jianpeng Du , Jian Liu , Jiangtao Li , Xiaohua Wang , Lin Zhang , Yalan Feng , Minglan Ma

An unprecedented metal-free cyclization reaction of tetralone-derived β-ketothioamides with nitroallylic acetates was developed, which provided a powerful method for the synthesis of 2,3-dihydrothiazole-5-carboxylates. In the reaction, nitroallylic acetates used α,β-carbons rather than the β,γ-carbons to construct the five-membered thiazole ring. The protocol features good functional group tolerance, mild metal-free conditions and simple procedure.

研究了四酮类β-酮硫酰胺与硝酸基乙酸酯的无金属环化反应，为2,3-二氢噻唑-5-羧酸酯的合成提供了有力的方法。在反应中，硝基乙酸酯用α、β-碳而不是β、γ-碳来构建五元噻唑环。该方案具有良好的官能团耐受性，温和的无金属条件和简单的程序。

引用次数: 0

Visible-light-induced ligand-to-metal charge transfer in synergistic catalysis with earth-abundant 3d transition metals: A new paradigm for sustainable organic synthesis 可见光诱导配体到金属的电荷转移与地球丰富的三维过渡金属协同催化：可持续有机合成的新范式

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-13 DOI: 10.1016/j.tet.2025.135087

Siyi Qin , Mingyang Yang , Xun Yang, Jingshu Han, Haiyan Li, Wengui Duan, Lin Yu

Ligand-to-metal charge transfer (LMCT) photocatalysis has emerged as a transformative strategy in synthetic organic chemistry. This review summaries the synergistic integration of photoinduced LMCT processes with earth-abundant transition-metal catalysis, highlighting a sustainable paradigm that addresses longstanding challenges in organic synthesis. Unlike traditional photoredox systems that rely on expensive noble metal (such as ruthenium and iridium) complexes, LMCT photocatalysis utilizes complexes formed between organic ligands and first-row transition metals (iron, copper, cobalt, and lanthanide cerium), which generate reactive radical intermediates under mild conditions upon visible light irradiation. The combination of LMCT photocatalysis with transition-metal catalysis creates powerful dual platforms that enable challenging transformations by merging radical-generating capabilities with the coordination and bond-forming abilities of nickel, copper, cobalt, manganese, chromium, and titanium catalysts. These systems operate through sophisticated mechanisms where photogenerated radical species interact with transition metal centers to access novel reaction pathways inaccessible to either catalytic system alone. This review analyzes recent developments in dual LMCT/transition-metal catalytic systems, examining their mechanisms, substrate scope, functional group compatibility, and synthetic utility. We highlight how these sustainable catalytic platforms have enabled challenging cross-coupling reactions, C–H functionalizations, and cascade transformations under remarkably mild conditions. Finally, we discuss current limitations and opportunities in this rapidly evolving field, with particular emphasis on expanding reaction scope, enhancing stereoselectivity, and advancing green chemistry principles.

配体到金属电荷转移（LMCT）光催化已成为合成有机化学中一种革命性的策略。本文综述了光诱导LMCT过程与地球上丰富的过渡金属催化的协同整合，强调了一个可持续的范例，解决了有机合成中长期存在的挑战。与依赖昂贵的贵金属（如钌和铱）配合物的传统光氧化还原系统不同，LMCT光催化利用有机配体与第一排过渡金属（铁、铜、钴和镧系铈）之间形成的配合物，在可见光照射下温和条件下产生反应性自由基中间体。LMCT光催化与过渡金属催化的结合创造了强大的双平台，通过将自由基生成能力与镍、铜、钴、锰、铬和钛催化剂的协调和成键能力相结合，实现了具有挑战性的转化。这些系统通过复杂的机制运作，其中光生成的自由基与过渡金属中心相互作用，从而获得单独催化系统无法获得的新反应途径。本文综述了近年来LMCT/过渡金属双催化体系的研究进展，探讨了其机理、底物范围、官能团相容性和合成用途。我们强调了这些可持续的催化平台如何在非常温和的条件下实现具有挑战性的交叉偶联反应，C-H功能化和级联转化。最后，我们讨论了这个快速发展的领域目前的局限性和机遇，特别强调了扩大反应范围，增强立体选择性和推进绿色化学原则。

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引用次数: 0

Investigation of the N2-Selective functionalization reaction of 2H-1,2,3-triazole catalyzed by a synergistic combination of copper and diamine ligands 铜与二胺配体协同组合催化2h -1,2,3-三唑n2选择性功能化反应的研究

IF 2.2 3区化学 Q2 CHEMISTRY, ORGANIC

Tetrahedron

Pub Date : 2025-12-13 DOI: 10.1016/j.tet.2025.135099

Aigui Zhang, Wenjing Luo, Zhonghua Qu, Weiqing Yang, Min Luo, Xin Li, Menglin Ma

N-Aryl-1,2,3-triazole compounds are important pharmaceutical motifs synthesized via nucleophile reactions with triazoles. Typically, both N² and N¹ regioisomers are produced simultaneously. In this article, a synergistic catalytic system comprising CuI and 1,2-diphenylethylenediamine (DPEN) was employed for the selective N²-coupling of 2-bromobenzoic acid with triazole. This reaction yielded 2-(2H-1,2,3-triazol-2-yl)benzoic acid (4a) with an impressive yield of 86 % and a regioselectivity of 91 % for the N² isomer. Additionally, 2-bromobenzoic acid served as a cost-effective alternative to the traditionally used 2-iodobenzoic acid; notably, the reaction time was reduced from 4 h to 1.5 h. Mechanistic studies indicated that the DPEN ligand promotes carbon-copper bond formation, enhancing reaction activity and accelerating the overall rate; However, while there has been some improvement in N² selectivity, it remains less than ideal.

n -芳基-1,2,3-三唑化合物是与三唑通过亲核反应合成的重要药物基序。通常，N2和N1区域异构体同时产生。本文采用由CuI和1,2-二苯乙二胺（DPEN）组成的协同催化体系进行了2-溴苯甲酸与三唑的选择性n2偶联反应。该反应生成2-（2h -1,2,3-三唑-2-基）苯甲酸（4a），其N2异构体的产率为86%，区域选择性为91%。此外，2-溴苯甲酸作为传统上使用的2-碘苯甲酸的一种具有成本效益的替代品；反应时间由4 h缩短至1.5 h。机理研究表明，DPEN配体促进了碳铜键的形成，提高了反应活性，加快了反应的总速率；然而，虽然对N2的选择性有了一定的提高，但仍然不够理想。

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