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Recent Applications of Radical Cascade Cyclization in the Synthesis of 2‐Functionalized Thioflavones 自由基级联环化在2-官能化硫代黄酮合成中的最新应用
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.70182
Jia‐Nan Chen , Yanli Yin , Fan‐Lin Zeng , Teck‐Peng Loh
Radical cascade cyclization reactions are widely employed in the synthesis of functionalized heterocycles due to their numerous advantages. This review carefully compiles and analyzes recent advancements in the construction of 2‐functionalized thioflavones through radical cascade cyclization reactions, emphasizing their potential and versatility in generating a range of valuable thioflavone products. These strategies enable the efficient synthesis of diverse 2‐functionalized thioflavones via heat‐ or light‐promoted reactions using methylthiolated alkynones as the acceptor substrate. In this review, we aim to provide a thorough overview of the state‐of‐the‐art approaches by exploring the mechanisms and scope of these reactions, while serving as a vital reference for future research and industrial applications in thioflavones synthesis.
自由基级联环化反应由于其诸多优点被广泛应用于官能化杂环的合成。本文综述和分析了通过自由基级联环化反应构建2功能化硫黄酮的最新进展,强调了它们在生成一系列有价值的硫黄酮产品方面的潜力和多功能性。这些策略使得以甲基硫代炔诺酮为受体底物,通过热催化或光催化反应有效地合成了多种2功能化的硫代黄酮类化合物。在本文中,我们旨在通过探索这些反应的机制和范围来全面概述最新的方法,同时为未来的研究和工业应用提供重要的参考。
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引用次数: 0
Synthesis of Trifluoromethyl‐Substituted Tetrazoles via KI/TBHP‐Mediated Oxidative Annulation of Trifluoroacetimidohydrazides and Nitromethane KI/ tbhp介导的三氟乙酰胺酰肼和硝基甲烷氧化环化合成三氟甲基取代四唑
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.70204
Jian Chen , Zijian Wang , Zhengkai Chen
A metal‐free strategy for the preparation of trifluoromethyl‐substituted tetrazoles via KI/TBHP‐mediated oxidative annulation of readily available trifluoroacetimidohydrazides (TFAIHs) and nitromethane has been disclosed. In this transformation, CH3NO2 is applied as both the inexpensive nitrogen synthon and reaction solvent, providing a straightforward access to a library of functionalized tetrazoles in moderate to good yields. Two plausible reaction pathways have been proposed on the basis of the preliminary mechanistic observations. The reaction could be scaled up to a 5 mmol scale and be applied to synthesize the key skeleton of GR205771, which is an orally active antiemetic NK1 receptor antagonist.
公开了一种通过KI/ thbhp介导的易得的三氟乙酰咪唑(TFAIHs)和硝基甲烷的氧化环法制备三氟甲基取代四唑的无金属策略。在这个转化中,CH3NO2被用作廉价的氮合成物和反应溶剂,提供了一个简单的途径,以中等到较高的收率获得功能化四唑库。根据初步的机理观察,提出了两种合理的反应途径。该反应可扩大到5 mmol的规模,并可用于合成口服抗吐NK1受体拮抗剂GR205771的关键骨架。
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引用次数: 0
Synthesis of Novel 1,4‐Diazepane‐Spirooxindole Frameworks via Catalytic (6 + 1) Annulation of Diazooxindoles with Hexahydropyrimidines 六氢嘧啶催化(6 + 1)环法制备1,4-二氮杂环-螺恶哚新框架
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500587
Xiaoai Liu , Songyi Gao , Chao Peng , Yu Xiong , Ye Guo , Ming Lang , Shiyong Peng
Herein, we have developed a catalytic (6 + 1) annulation of diazooxindoles with hexahydropyrimidines under rhodium or copper catalysis. This strategy offers a general and efficient method for constructing pharmacologically relevant 1,4‐diazepane‐spirooxindole frameworks in moderate to excellent yields. Diverse synthetic transformations of the obtained products have also been achieved to obtain more complex and even drug‐like spirooxindoles, demonstrating the broad synthetic utility of this approach.
在此,我们在铑或铜的催化下,开发了重氮唑酮与六氢嘧啶的催化(6 + 1)环。该策略为构建具有药理意义的1,4-二氮平-螺菌吲哚框架提供了一种通用且高效的方法。所获得的产物的多种合成转化也已实现,以获得更复杂甚至类似药物的螺菌吲哚,证明了该方法的广泛合成实用性。
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引用次数: 0
Trifluoroacetic Acid‐Mediated Cyclization of α‐Mercapto Ketones with Trifluoromethyl N‐Acylhydrazones for the Synthesis of 2‐Trifluoromethylthiazole Derivatives 三氟乙酸介导α-巯基酮与三氟甲基n -酰基腙环化合成2-三氟甲基噻唑衍生物
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.70213
Assoc. Prof. Junjiao Wang , Xiujuan Zhao , Yinzhu Wang , Yang Li , Kaijian Zhu , Na Wang , Prof. Danfeng Huang , Assoc. Prof. Ke‐Hu Wang , Prof. Yulai Hu
A novel method for synthesizing fully substituted 2‐trifluoromethylthiazoles is reported, achieving yields up to 94% via trifluoroacetic acid (TFA)‐mediated intermolecular cyclization of α‐mercapto ketones with trifluoromethyl N‐acylhydrazones under mild, open‐flask conditions. This reaction involves cleavage of the N–N bond in the acylhydrazone moiety, and efficiently constructs dual carbon‐heteroatom bonds of C─N and C─S in one step. The protocol features broad substrate scope, operational simplicity, and scalability, as demonstrated by a gram‐scale synthesis.
报道了一种合成完全取代的2-三氟甲基噻唑的新方法,在温和的开瓶条件下,通过三氟乙酸(TFA)介导的α-巯基酮与三氟甲基n-酰基腙的分子间环化,收率高达94%。该反应通过破坏酰基腙部分的N - N键,一步高效地构建C─N和C─S的碳杂原子双键。该协议具有广泛的基板范围,操作简单和可扩展性,如克级合成所示。
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引用次数: 0
10‐Azidotetrazolo[1,5‐a][1,10] Phenanthroline: A Case of Azido‐tetrazole Behavior in 1,10‐Phenanthroline with Unusual Molecular Structure 10-叠氮四唑[1,5- A][1,10]菲罗啉:分子结构异常的1,10-菲罗啉中叠氮四唑行为的一个例子
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500592
Yong Qiang Wan , Shi Lin Zhang , Yang‐Yang Zhang , Zeng Yuan Li , Xinyi Shi , Prof. John F. Gallagher , Prof. Jun Li , Prof. Pavle Mocilac
In our quest for novel An/Ln separating ligands, we have synthesized a heterocyclic precursor based on phenanthroline and identified it as 10‐azidotetrazolo[1,5‐a][1,10] phenanthroline. This asymmetric heterocyclic azide has been synthesized in four reaction steps in good yield and is well characterized via experimental methods. Thermal analysis shows that this compound is reasonably stable as an azide. The heterocycle shows fluorescent properties with a distinctive red shift of the emissions and excitation peaks. A single‐crystal XRD study shows that the molecule is planar and exhibits total molecular disorder with molecules in the crystal structure present in a major:minor conformation ratio of 0.91:0.09 and related by a 180° flip. In addition, quantum‐theoretical investigation suggests that such a product with one fused tetrazolo ring is the most stable one out of other alternatives. This molecule presents a relatively rare case of azido‐tetrazole tautomerism in 1.10‐phenanthroline.
在寻找新的An/Ln分离配体的过程中,我们合成了一种基于菲罗啉的杂环前体,并鉴定为10-叠氮四唑[1,5-a][1,10]菲罗啉。该不对称杂环叠氮化合物经四个反应步骤合成,收率高,并通过实验方法进行了表征。热分析表明该化合物作为叠氮化物是相当稳定的。杂环具有明显的发射峰和激发峰红移的荧光特性。单晶XRD研究表明,该分子呈平面状,整体分子结构无序,晶体结构中分子的主、次构象比为0.91:0.09,并以180°翻转关系存在。此外,量子理论研究表明,这种具有一个熔融四唑环的产品是其他替代品中最稳定的产品。该分子在1.10-菲罗啉中呈现相对罕见的叠氮-四唑互变异构。
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引用次数: 0
Palladium‐Catalyzed Cascade Intramolecular Cyclization/Intermolecular Michael Addition Reaction of Allenyl Benzoxazinones with 3‐Aroylcoumarins 钯催化丙烯基苯并恶嗪酮与3-芳基香豆素的级联分子内环化/分子间Michael加成反应
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.70202
Jiayi Luo , Shengbiao Yang , Bing Han , Yanshuo Liu , Jincheng Li , Ran Wang , Baochuan Guan , Chunhao Yuan
4‐Alkyl coumarins and 2‐alkyl quinolines exhibit significant biological activities. Connecting these two molecular frameworks via an alkyl chain represents a promising strategy for developing novel bioactive compounds. However, research in this area remains relatively limited. Recently, a Pd(0) π‐Lewis base‐catalyzed C─C coupling strategy has emerged as an efficient method for coupling such molecules. In this study, we report a palladium‐catalyzed cascade reaction involving intramolecular cyclization and intermolecular Michael addition between allenyl benzoxazinones and 3‐aroylcoumarins. The process initiates with the Pd‐mediated formation of η2‐Pd complexes from allenyl benzoxazinones, which subsequently undergo C─C coupling with 3‐aroylcoumarins, enabling efficient access to a diverse series of 4‐(quinolin‐2‐ylmethyl)coumarin derivatives.
4-烷基香豆素和2-烷基喹啉具有显著的生物活性。通过烷基链连接这两个分子框架代表了一种开发新型生物活性化合物的有前途的策略。然而,这方面的研究仍然相对有限。近年来,Pd(0) π-Lewis碱催化的C─C偶联策略成为一种有效的偶联方法。在这项研究中,我们报道了钯催化的级联反应,包括烯基苯并恶嗪酮和3-芳基香豆素之间的分子内环化和分子间Michael加成。该过程始于烯基苯并恶嗪酮在pd介导下形成η -2- pd配合物,随后与3-芳基香豆素进行C─C偶联,从而有效地获得多种4-(喹啉-2-甲基)香豆素衍生物。
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引用次数: 0
Metal‐Free Direct Esterification of Aldehydes Using Hydroxylamine‐O‐Sulfonic Acid 羟胺-邻磺酸催化醛类无金属直接酯化
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500602
Ashirwad Divedi , Jawahar L. Jat
Ester synthesis has traditionally depended on expensive metal catalysts and harsh reaction conditions. Despite the widespread use of these methods, challenges remain in the efficient synthesis of substituted esters. Here, we present a new metal‐free esterification method, in which hydroxylamine‐O‐sulfonic acid (HOSA) reacts with aldehydes in the presence of alcohols to produce alkyl alkanoates or benzoates. The reaction proceeds via in situ generation of nitrile and imidate intermediates. This method affords esters of aliphatic, aromatic, polycyclic, and heteroaromatic aldehydes in good to excellent yields and tolerates a variety of functional groups
传统上,酯的合成依赖于昂贵的金属催化剂和苛刻的反应条件。尽管这些方法被广泛使用,但在取代酯的有效合成方面仍然存在挑战。在这里,我们提出了一种新的无金属酯化方法,其中羟胺-邻磺酸(HOSA)与醛在醇的存在下反应生成烷基烷酸酯或苯甲酸酯。该反应通过原位生成腈和酰亚胺中间体进行。这种方法提供脂肪族、芳香族、多环和杂芳香醛的酯,产率好到极好,并且可以耐受各种官能团
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引用次数: 0
Efficient Synthesis of Propylene Carbonate over Bimetallic Fe─Cu/SBA‐15 Catalyst from CO2 and Propylene Oxide CO2和环氧丙烷催化双金属Fe─Cu/SBA-15高效合成碳酸丙烯
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500432
Akash Mandal , Neelanjana Ghosh , Bhabani Malakar , Dileep Kumar , Vipin Amoli , Asim Bhaumik , Biswajit Chowdhury
The direct synthesis of propylene carbonate (PC) from propylene oxide (PO) and carbon dioxide (CO2) without the use of solvents was investigated utilizing bimetallic Fe─Cu/SBA‐15 catalysts. The Fe─Cu/SBA‐15 catalyst was prepared using the sol–gel method and was thoroughly characterized for understanding the nanostructure, morphology, and chemical composition. The catalytic performance was assessed under mild reaction conditions, specifically at atmospheric CO2 pressure, using PO as the substrate. Key reaction parameters, including temperature, catalyst dosage, and reaction time, were systematically optimized. Among the catalysts tested, 5 Fe─Cu/SBA‐15 exhibited superior activity, achieving an impressive PO conversion of 87% and PC selectivity of 95% under optimized conditions. The addition of tetrabutylammonium bromide (TBAB) as a co‐catalyst is necessary for obtaining maximum product yields. Further, the synergistic interaction between Fe and Cu was investigated, revealing that both metal species serve as active sites in catalysis. This bimetallic mesoporous material shows high recyclability for the PC synthesis, suggesting a wider scope of this work.
以双金属Fe─Cu/SBA-15为催化剂,研究了环氧丙烷(PO)和二氧化碳(CO2)在不使用溶剂的情况下直接合成碳酸丙烯(PC)的反应。采用溶胶-凝胶法制备了Fe─Cu/SBA-15催化剂,并对其纳米结构、形貌和化学成分进行了表征。在温和的反应条件下,特别是在大气CO2压力下,以PO为底物,评估了催化性能。对反应温度、催化剂用量、反应时间等关键参数进行了系统优化。在测试的催化剂中,5fe─Cu/SBA-15表现出优异的活性,在优化条件下,PO转化率达到87%,PC选择性达到95%。添加四丁基溴化铵(TBAB)作为助催化剂是获得最大产率的必要条件。此外,研究了Fe和Cu之间的协同作用,揭示了这两种金属都是催化的活性位点。这种双金属介孔材料在PC合成中具有较高的可回收性,表明本研究具有更广泛的应用前景。
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引用次数: 0
Cs2CO3‐Mediated [3 + 3] Cyclization of 2‐Amino‐4H‐chromen‐4‐ones and Benzylidene Meldrum's Acids: Access to Chromeno[2,3‐b]pyridinones cs2co3介导的2-氨基- 4h -4- 1和苄基Meldrum酸的[3 + 3]环化:获得Chromeno[2,3-b]吡啶酮
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.70205
Jiaman Lv , Wenyan Zhou , Prof. Ziyang Zhang , Dr. Lizhong Wang , Prof.Dr. Jiaming Liu , Cunde Wang
An [3 + 3] annulation of 2‐aminochromen‐4‐ones with substituted benzylidene Meldrum's acids has been developed. This reaction included a sequential intermolecular Michael addition/intramolecular nucleophilic addition/ring opening of Meldrum's acid/ removal of acetone/decarboxylation sequence, which possessed excellent step in a single operation for direct generating to substituted chromeno[2,3‐b]pyridinones from readily available substrates.
用取代苄基梅尔德鲁姆酸制备了2-氨基色素-4- 1的[3 + 3]环。该反应包括分子间Michael加成反应/分子内亲核加成反应/ Meldrum酸开环反应/丙酮脱除反应/脱羧反应,该反应在一次操作中直接从现成的底物生成取代的[2,3-b]吡啶酮。
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引用次数: 0
Core@shell Nanostructured Catalysts: Implementation in Organic Transformations Core@shell纳米结构催化剂:在有机转化中的实现
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500529
Mohammadreza Shokouhimehr , Dokyoon Kim , M. Toufiq Reza
The demand for novel nanostructured catalysts to expedite organic transformations, including amination, Suzuki reactions, oxidation, and reduction, has been growing significantly for practical purposes in recent decades. The variability of core@shell nanostructured catalysts (CSNCs) has enabled the development of their novel implementations in sustainable and lucrative organic transformations. This perspective article delineates current advancements in the synthetic methodologies of specific CSNCs and their catalytic efficacy in selected organic reactions, such as amination, reduction, oxidation, Suzuki cross‐coupling, etc. Discussions explore the approaches and illustrations for the recyclable CSNCs, including their benefits and shortcomings, sustainability, and the effectiveness of the stated catalysts in the specified organic transformations. In addition, advancements in synergistic interactions between the cores and shells in CSNCs and sustainable systems using magnetic components for recycling techniques strove to enhance catalytic efficiency and provide cost‐effective catalysts for specific transformations.
对新型纳米结构催化剂的需求,以加快有机转化,包括胺化,铃木反应,氧化和还原,已经在近几十年的实际用途显著增长。core@shell纳米结构催化剂(CSNCs)的可变性使其在可持续和有利可图的有机转化中的新实现得以发展。本文综述了近年来特定CSNCs的合成方法及其在胺化、还原、氧化、铃木交叉偶联等有机反应中的催化效果。讨论探讨了可回收CSNCs的方法和实例,包括它们的优点和缺点,可持续性以及在所述催化剂在特定有机转化中的有效性。此外,CSNCs中核和壳之间的协同相互作用以及使用磁性元件进行回收技术的可持续系统的进展努力提高催化效率,并为特定转化提供具有成本效益的催化剂。
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引用次数: 0
期刊
Asian Journal of Organic Chemistry
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