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Harnessing Functionalized Alkynes in Annulation Reactions: A Comprehensive Review 环化反应中功能化炔的应用综述
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70290
Nandini B. Kale , Mary Sravani Galla , Nagula Shankaraiah
Functionalized alkynes have emerged as pivotal entities in modern synthetic chemistry and also exhibit as versatile building blocks toward the construction of diverse molecular frameworks. This review emphasizes a comprehensive overview of recent advancements in the applications of functionalized alkynes, such as ynals, ynamides, alkynols, diynes, and miscellaneous alkynes in annulation reactions. The review also discussed the utility of functionalized alkynes from traditional organic synthesis to innovative metal‐mediated transformations, late‐stage functionalization of complex molecules, medicinal chemistry, including natural products and pharmaceuticals.
功能化炔在现代合成化学中已经成为关键的实体,并且在构建各种分子框架方面也表现出多功能的基础。本文综述了功能化炔类化合物在环化反应中的应用进展,如炔类、酰胺类、炔醇类、二炔类和杂炔类。综述还讨论了功能化炔烃的应用,从传统的有机合成到创新的金属介导转化,复杂分子的后期功能化,药物化学,包括天然产物和药物。
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引用次数: 0
[4+2] Annulation Reaction of Indole‐2‐Carboxamides With Vinylsulfonium Salts: Synthesis of Pyrazinoindolones [4+2]吲哚-2-羧基酰胺与乙烯基磺酸盐的环化反应:吡嗪吲哚酮的合成
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70304
Wei Wang , Rongrong Li , Yuexiu Cao , Li Wang , Jinying Cao , Peng Qian , Yannan Zhu
A base‐promoted [4+2] annulation reaction between indole‐2‐carboxamides and vinylsulfonium salts has been developed, affording the pyrazinoindolones in 39%–96% yields with high chemoselectivity. The synthesis strategy of vinylsulfonium salts can also approach to benzimidazole‐fused azabicyclo[3.1.0]hexanes via a [3+2]/[2+1] annulation process with benzimidazole‐derived acrylonitriles as the reaction partners.
研究了吲哚-2-羧胺与乙烯基磺酸盐之间的碱促进[4+2]环化反应,得到了产率为39% ~ 96%的吡嗪吲哚酮,并具有较高的化学选择性。乙烯基磺酸盐的合成策略也可以通过以苯并咪唑衍生的丙烯腈为反应伙伴,采用[3+2]/[2+1]环法制备苯并咪唑-偶氮杂环[3.1.0]己烷。
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引用次数: 0
Experimental and Computational Study of Pyridine Carboxylate Ionic Liquid‐Mediated Knoevenagel Condensation at Ultralow Loadings 超低负荷下羧酸吡啶离子液体介导Knoevenagel缩合的实验与计算研究
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.202500635
Hiren Jungi , Sumana Podder , Dheeraj Kumar , R. S. Malavika , Rositha Kuniyil , Joyee Mitra
Knoevenagel condensation reaction is a crucial C─C bond formation reaction in organic synthesis, providing access to diverse biological and industrial intermediates. Although catalyst‐free protocols for this reaction have been explored, they often suffer from sluggish kinetics and limited substrate scope, typically restricted to aromatic aldehydes. Herein, we explore a family of basic ionic liquids (ILs) synthesized from naturally occurring pyridine carboxylic acid as an organocatalyst for Knoevenagel condensation. The presence of a carboxylate group adjacent to pyridine in the catalyst significantly enhances its efficiency, enabling solvent‐free reactions under mild conditions, with ultralow IL loadings (∼ 0.2 mol%). DFT calculations revealed that the pyridine‐assisted pathway is energetically favorable compared to the carboxylate‐mediated route. The designed system is an efficient and reusable organocatalyst for Knoevenagel condensation, catering to a broad substrate scope including aromatic, heterocyclic, and less electrophilic aliphatic aldehydes. Moreover, this protocol enables the green synthesis of bioactive tetrahydrobenzo[b]pyrans via a one‐pot, three‐component reaction. Calculated green metrics further validated the practical applicability of the catalytic protocol, toward the sustainable production of industrially relevant molecules, as the calculated E‐factor value of 0.16 aligns with reported IL‐based green protocols.
Knoevenagel缩合反应是有机合成中重要的C─C键形成反应,提供了多种生物和工业中间体的途径。虽然已经探索了该反应的无催化剂方案,但它们通常受到动力学缓慢和底物范围有限的影响,通常仅限于芳香族醛。本文中,我们探索了一类碱性离子液体(ILs),它们是由天然存在的吡啶羧酸作为Knoevenagel缩合的有机催化剂合成的。在催化剂中邻近吡啶的羧酸基团的存在显著提高了其效率,在温和的条件下实现无溶剂反应,具有超低的IL负载(~ 0.2 mol%)。DFT计算表明,与羧酸盐介导的途径相比,吡啶辅助途径在能量上更有利。所设计的系统是一种高效且可重复使用的Knoevenagel缩合有机催化剂,适用于广泛的底物范围,包括芳香族、杂环和亲电性较低的脂肪族醛。此外,该方案通过一锅三组分反应实现了生物活性四氢苯并芘的绿色合成。计算出的绿色指标进一步验证了催化方案在工业相关分子可持续生产方面的实际适用性,因为计算出的E因子值为0.16,与报道的基于IL的绿色方案一致。
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引用次数: 0
Transition‐Metal Free Dialkylation to Construct All‐Carbon Quaternary Centers From Alkyl Chlorides and 1,3‐Dicarbonyl Compounds 由氯烷基和1,3-二羰基化合物制备全碳季中心的过渡金属游离二烷基化反应
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70276
Wenjing Liu , Feng Zhao
A practical and efficient potassium trimethylsilanolate/nitrile system for constructing all‐carbon quaternary centers has been developed. This transition‐metal free protocol utilizes readily available chlorides and 1,3‐dicarbonyl compounds, enabling the selective formation of two C─C bonds in a single operation. The reaction features broad substrate scope, good functional group tolerance, large scale synthesis, and further structural modification, providing a mild approach to access quaternary centers in moderate to excellent yields.
开发了一种实用高效的三甲基硅酸钾/腈体系,用于构建全碳季中心。这种不含过渡金属的方案利用现成的氯化物和1,3-二羰基化合物,能够在一次操作中选择性地形成两个C─C键。该反应具有底物范围广、官能团耐受性好、大规模合成和进一步的结构修饰等特点,为以中等至优异收率获得季中心提供了一种温和的途径。
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引用次数: 0
Iridium‐Catalyzed Anti‐Stereoselective Ring‐Opening Fluoroalkoxylation of Heterobicyclic Alkenes 铱催化杂双环烯烃反立体选择开环氟烷氧基化
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70274
Dandan Zhao , Hongyan Yang , Xiaoli Wang , Peng He , Yanli Xu , Qifu Lin
A highly efficient iridium‐catalyzed ring‐opening reactions of heterobicyclic alkenes with fluoroalkyl alcohols has been developed. The reaction utilizes readily available fluoroalkyl alcohols as fluoroalkoxylation reagents and exhibits a wide substrate scope, affording the fluoroalkoxylated products with trans‐1,2‐disubstituted dihydronaphthalene framework in good to excellent yields. Mechanistic insights, supported by computational studies, have been proposed to elucidate the reaction pathway.
研究了一种铱催化杂双环烯烃与氟烷基醇开环的高效反应。该反应利用易于获得的氟烷基醇作为氟烷氧基化试剂,并具有广泛的底物范围,可提供具有反式-1,2-二取代二氢萘骨架的氟烷氧基化产物,收率高至高。在计算研究的支持下,已经提出了阐明反应途径的机制见解。
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引用次数: 0
Electrochemical Oxidative N–N Coupling to Construct Benzo[c]cinnolines and Azoarenes 电化学氧化N-N偶联制备苯并[c]喹啉和偶氮芳烃
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70271
Shiyun Li , Yan An , Lulu Wang , Xin Li , Yao Tan , Bin Wen , Tiesen Li , Xingquan Chen
A highly efficient electrochemical oxidative dehydrogenative N–N coupling of arylamines to selectively provide benzo[c]cinnolines and azoarenes has been investigated. In this simple process, various functional groups were tolerated under mild reaction conditions without additional metal or oxidant, and the practicality of the protocol was demonstrated by the preparation of benzo[c]cinnolines on a gram scale and later derivatization. Mechanism of studies shows that the reaction proceeds via a radical pathway with the hydrazine compound as an intermediate. Additionally, the base plays an important role in this transformation, potentially facilitating the dehydrogenation process.
研究了芳胺的高效电化学氧化脱氢N-N偶联选择性制备苯并[c]喹啉和偶氮芳烃。在这个简单的过程中,各种官能基团在温和的反应条件下被耐受,没有额外的金属或氧化剂,并且通过制备克级苯并[c]肉桂碱和随后的衍生化证明了该方案的实用性。机理研究表明,该反应以肼化合物为中间体,通过自由基途径进行。此外,碱在这种转化中起着重要作用,可能促进脱氢过程。
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引用次数: 0
Maleimides as Versatile Reactive Platforms in Transition‐Metal‐Catalyzed C–H Activation/Annulation 马来酰亚胺作为过渡金属催化碳氢活化/环化的通用反应平台
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70294
Divya Shrestha , Karuna Mahato , Prasanta Roy , Seung Woo Lee , Yong Rok Lee
Maleimide‐containing molecules serve as important scaffolds for biological activities as well as photochemical properties and play a significant role in both the academic and industrial communities. Maleimides are versatile coupling partners owing to their diverse reactivities with transition‐metal catalysts in C–H activation and annulation reactions including alkenylation, alkylation, fused‐annulation, and spiro‐annulation for the synthesis of numerous maleimide‐containing bioactive molecules such as succinamides, lactams, and lactims. In this review, innovative advances toward the synthesis of biologically important maleimide/succinimide‐bearing scaffolds through C–H activation and annulation reactions with transition metal as catalysts, with particular emphasis on the intermediates, transition states, and incorporation of different annulation sites for maleimide is reviewed. This review covers research published between 2019 and 2025, highlighting the substrate scope, reaction mechanisms, synthetic transformations, and future prospects of this approach.
含马来酰亚胺分子是生物活性和光化学性质的重要支架,在学术界和工业界都发挥着重要作用。马来酰亚胺是一种多用途的偶联剂,因为它们在C-H活化和环化反应中与过渡金属催化剂具有不同的反应活性,包括烯烃化、烷基化、融合环化和螺环化,用于合成许多含马来酰亚胺的生物活性分子,如琥珀酰胺、内酰胺和内酰胺。本文综述了以过渡金属为催化剂,通过C-H活化和环化反应合成具有重要生物学意义的马来酰亚胺/琥珀酰亚胺支架的新进展,重点介绍了中间体、过渡态和马来酰亚胺不同环化位点的合成。本文综述了2019年至2025年间发表的研究成果,重点介绍了底物范围、反应机制、合成转化以及该方法的未来前景。
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引用次数: 0
mpg‐CN Photo‐Catalyzed Annulation of 2‑Isocyanobiaryls With Silanes to 6‑Silyl‐Substituted Phenanthridines 光催化2 -异氰基双芳烷与硅烷环化合成6 -硅基取代菲咯啶
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70299
Xuehua Zhang , Jie Gao , Binyu He , Mengtian Dong , Tiankai Zhang , Jun Dong , Feng Chen
This work presents a visible‐light‐driven annulation protocol for synthesizing 6‐silylphenanthridines from 2‐isocyanobiaryls and silanes using mesoporous graphitic carbon nitride (mpg‐CN) as a heterogeneous photocatalyst. The mpg‐CN catalyst demonstrates exceptional recyclability, maintaining consistent activity over five consecutive cycles without loss of performance. Operating under ambient conditions without requiring precious metals or expensive organic photo redox catalysts, this method offers mild reaction conditions, cost efficiency, and operational simplicity. The protocol provides a scalable and sustainable approach to accessing 6‐silyl‐substituted phenanthridines, highlighting the potential of heterogeneous photocatalysis in organic synthesis.
本研究提出了一种以介孔石墨氮化碳(mpg-CN)为非均相光催化剂,由2-异氰基双芳基和硅烷合成6-硅基菲菲啶的可见光驱动环化方案。mpg-CN催化剂表现出卓越的可回收性,在连续五个循环中保持稳定的活性而不损失性能。该方法在环境条件下操作,不需要贵金属或昂贵的有机光氧化还原催化剂,反应条件温和,成本效益高,操作简单。该协议提供了一种可扩展和可持续的方法来获取6-硅基取代的菲菲啶,突出了异相光催化在有机合成中的潜力。
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引用次数: 0
Optically Active 2‐Azatriptycene Bearing a 1‐Pyrenyl Unit Exhibiting Acid‐Induced CPL Switching With Sign Inversion 含1-芘基的光学活性2-叠氮甲烯显示酸诱导CPL转换和符号反转
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70297
Yusuke Hashimoto , Ryo Inoue , Masayuki Gon , Kazuo Tanaka , Norihiro Aiga , Satoshi Takeuchi , Kazuya Kubo , Tomohiro Agou
Optically active 2‐azatriptycene 1 bearing a 1‐pyrenyl unit was synthesized. The resolved enantiomers exhibited blue circularly polarized luminescence (CPL) in solution, with dissymmetry factor glum on the order of 10−4–10−5. In contrast, the corresponding protonated species 1H+ exhibited green CPL with reversed sign, demonstrating that optically active 2‐azatriptycene functions as an acid‐responsive chiral switching unit.
合成了具有光学活性的含1-芘基的2-氮杂三烯1。对映体在溶液中表现出蓝色圆偏振发光(CPL),不对称因子glum为10−4 ~ 10−5。相反,对应的质子化产物1H+呈现出绿色的CPL,其符号相反,这表明2-叠氮三烯具有旋光性,是一种酸反应性的手性开关单元。
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引用次数: 0
Y‐Aromatic Guanidines as Steering Reagent in Multicomponent Heterocyclic Syntheses y -芳香族胍在多组分杂环合成中的导向作用
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-01 DOI: 10.1002/ajoc.70311
Yatharth Joshi , Manorama Singh , Ankita Rai , Vijai K. Rai
The organic compounds containing guanidine moieties are known to show several applications in the field of medicines, catalysts, and polymers, etc. The use of guanidines has been explored by researchers all over the world. Guanidines serve as an important tool in the synthesis of heterocycles, which serve as therapeutic agents and also show a wide array of applications. Due to their cost efficiency, atom economy, and eco‐friendliness, Multicomponent reactions (MCRs) have drawn the attention of researchers and scientists all over the world. This review highlights the applications of guanidines as a reagent as well as a catalyst in synthesizing various heterocyclic scaffolds via one‐pot Multicomponent reactions.
已知含有胍基的有机化合物在药物、催化剂和聚合物等领域具有广泛的应用。胍类药物的使用已被世界各地的研究人员所探索。胍类化合物是合成杂环化合物的重要工具,具有广泛的应用前景。多组分反应(Multicomponent reactions, mcr)因其成本效益、原子经济性和生态友好性而受到世界各国研究人员和科学家的关注。综述了胍类化合物作为催化剂和试剂在一锅多组分反应合成各种杂环支架中的应用。
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引用次数: 0
期刊
Asian Journal of Organic Chemistry
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