Asian Journal of Organic Chemistry最新文献

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1,2,4‐Oxadiazol‐5(4H)‐Ones: Versatile Building Blocks in Synthetic Chemistry 1,2,4‐Oxadiazol‐5（4H）‐Ones：合成化学中的多功能构建模块

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.70236

Zhiqing Huang , Hulin Zhong , Taile Li , Prof. Yang Gao , Prof. Yanping Huo , Prof. Qian Chen , Prof. Xianwei Li

The rapid construction of densely functionalized molecules through the exploration of versatile multitasking building blocks holds significant synthetic potential for pharmaceuticals, agrochemicals, and advanced materials. Among these, 1,2,4‐oxadiazol‐5(4H)‐ones have emerged not only as key scaffolds in biologically active molecules but also as highly adaptable synthons, enabling diverse synthetic transformations for the concise and selective assembly of functionalized architectures. Over the past decades, the reactivity profile of 1,2,4‐oxadiazol‐5(4H)‐ones has been greatly expanded, facilitating their use as O‐ or N‐nucleophiles, nitrogen sources for direct C–H functionalization, directing groups, and internal oxidizing directing groups. These attributes allow for the efficient synthesis of diverse heterocyclic systems and complex molecular frameworks under mild and sustainable conditions. This review comprehensively summarizes recent advances in the synthetic applications of 1,2,4‐oxadiazol‐5(4H)‐ones, covering their roles as bifunctional reagents, coupling partners, and redox‐active auxiliaries in transition‐metal‐catalyzed and metal‐free transformations. We also provide a critical outlook on future directions, including enantioselective catalysis, photoredox and electrochemical applications, and the integration of oxadiazolones in the synthesis of bioactive molecules and functional materials. It is anticipated that this review will inspire further innovation in the design and application of multitasking building blocks in synthetic chemistry.

通过探索多用途多任务构建块快速构建密集功能化分子，在药物、农用化学品和先进材料方面具有重要的合成潜力。其中，1,2,4‐恶二唑‐5（4H）‐不仅是生物活性分子的关键支架，而且是高度适应性的合成子，能够实现多种合成转化，以实现简洁和选择性的功能化结构组装。在过去的几十年里，1,2,4 -噻二唑- 5(4H) -酮的反应性已经得到了极大的扩展，这使得它们可以作为O -或N -亲核试剂、直接C-H功能化的氮源、导向基团和内部氧化导向基团。这些特性允许在温和和可持续的条件下有效地合成各种杂环系统和复杂的分子框架。本文综述了近年来1,2,4 -恶二唑- 5(4H) -酮类化合物在过渡金属催化和无金属转化中的应用，包括它们作为双功能试剂、偶联剂和氧化还原活性助剂的作用。展望了未来的发展方向，包括对映选择性催化、光氧化还原和电化学应用，以及恶二唑酮类化合物在生物活性分子和功能材料合成中的应用。期望本文的研究成果能够激发合成化学中多任务构建模块的设计和应用方面的进一步创新。

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引用次数: 0

Cyclopropenium Ion–Enabled Reductive Amination of Aldehydes With Indolines Without an External Hydride Source 环丙烯离子使醛与吲哚的还原胺化无外部氢化物源

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.202500607

Shaheen Fatma , Feroz Ahmad , Mahir , Chanda Pavan Kalyan , Ramasamy Vijaya Anand

The direct reductive amination of aldehydes and ketones with primary/secondary amines is the primary approach to the synthesis of substituted secondary and tertiary amines. Generally, an external reducing agent or a hydride source is required for this transformation. However, in the recent past, many efforts have been made to perform this transformation without the need for any external hydride sources. However, most of those protocols involve harsh conditions (very high temperature or the use of microwave). In this article, we demonstrate that one of the tris(aryl)cyclopropenium salts could be used as an organic Lewis acid catalyst for the reductive amination of aryl aldehydes with indolines without the use of any external hydride source. Basically, the cyclopropenium cation (as a Lewis acid) activates the carbonyl group of the aldehyde, and the reaction proceeds through the formation of the iminium ion followed by a hydride shift from the α‐carbon of another indoline to generate the desired amine. Unlike the other reported methods (without an external hydrogen source), this protocol worked well under milder conditions and many aryl aldehydes underwent reductive amination with indolines to provide the respective N‐benzyl indoline derivatives in moderate to good yields.

用伯胺或仲胺直接还原醛和酮的胺化反应是合成取代仲胺和叔胺的主要方法。一般来说，这种转变需要外部还原剂或氢化物源。然而，在最近的过去，已经做出了许多努力来完成这种转变，而不需要任何外部氢化物源。然而，这些协议大多涉及苛刻的条件（非常高的温度或使用微波）。在本文中，我们证明了其中一种三（芳基）环丙烯盐可以用作有机路易斯酸催化剂，在不使用任何外部氢化物源的情况下与吲哚进行芳基醛的还原胺化反应。基本上，环丙烯阳离子（作为路易斯酸）激活了醛的羰基，反应通过形成亚胺离子进行，然后从另一种吲哚的α -碳氢化物转移产生所需的胺。与其他报道的方法（没有外部氢源）不同，该方法在较温和的条件下工作得很好，许多芳醛与吲哚进行还原胺化反应，以中高产出相应的N -苄基吲哚衍生物。

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引用次数: 0

One‐Pot Sequential Heck–Suzuki Synthesis of 5‐Styryl‐9‐Hydroxy‐1H‐phenalen‐1‐ones with Tunable Optoelectronic Properties 具有可调谐光电性能的5 -苯乙烯- 9 -羟基- 1H -酚醛- 1 -化合物的一锅序步Heck-Suzuki合成

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.202500621

Sven Daniel , Prof. Dr. Thomas J. J. Müller

For the preparation of novel 5‐styryl‐substituted 9‐hydroxy‐1H‐phenalen‐1‐ones, a sequential Pd‐catalyzed Heck vinylenation–Suzuki arylation one‐pot strategy was established, providing efficient access to a library of donor–acceptor chromophores. These multifunctional conjugates are characterized by a planar, highly conjugated backbone extended through vinyl substitution at the 5‐position. The obtained compounds were comprehensively investigated with respect to their electrochemical and photophysical properties. Cyclic voltammetry demonstrates that the reduction potentials remain largely unaffected by substituents, whereas the oxidation potentials show a pronounced dependence on the electronic nature of the aryl groups. UV–vis and fluorescence spectroscopy revealed bathochromic shifts of absorption and emission maxima for electron‐donating substituents, while electron‐withdrawing groups induce hypsochromic responses. Complementary Hammett correlations confirm the dominance of resonance effects, with the strongest linear relationships observed for the extended σ_p+ parameter, highlighting mesomeric stabilization as the decisive factor in modulating electronic transitions. Quantum‐chemical (TD)DFT calculations reproduce the spectroscopic trends and provide detailed insight into orbital contributions and charge‐transfer characteristics. Solvatochromic analyses further evidence the polar nature of the excited states, supporting a pronounced intramolecular charge‐transfer character.

为了制备新的5 -苯乙烯基取代的9 -羟基-苯乙烯- 1 -苯乙烯，我们建立了一个顺序Pd催化的Heck乙烯基- suzuki芳基化一锅策略，提供了一个高效的供体-受体发色团库。这些多功能缀合物的特点是在5位通过乙烯基取代扩展了一个平面的、高度共轭的主链。对所得化合物的电化学和光物理性质进行了全面的研究。循环伏安法表明，还原电位在很大程度上不受取代基的影响，而氧化电位则明显依赖于芳基的电子性质。紫外-可见光谱和荧光光谱显示，供电子取代基的吸收和发射最大值发生了深变色变化，而吸电子取代基则引起了次变色反应。互补Hammett相关证实了共振效应的优势，扩展的σp+参数具有最强的线性关系，突出了中间体稳定是调制电子跃迁的决定性因素。量子化学（TD）DFT计算再现了光谱趋势，并提供了对轨道贡献和电荷转移特性的详细见解。溶剂致变色分析进一步证明了激发态的极性性质，支持分子内电荷转移的显著特征。

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引用次数: 0

Structural Modifications to Fine Tune the Redox Characteristics of Catenane 结构修饰以微调链烷的氧化还原特性

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.70257

Kongki Gogoi , Pavan Kumar Matsa , Gowtami Allada , Sourav Chakraborty

Catenanes, an intriguing class of mechanically interlocked molecules (MIMs), have garnered substantial attention due to their dynamic redox‐responsive behaviors and unique topological architectures. The interlocked nature of these systems allows precise control of molecular motion under electrochemical stimuli, which is valuable in designing molecular machines and devices. This review highlights contemporary advancements in the structural modification of catenanes to fine‐tune their redox properties. Emphasis is placed on how changes in substitution patterns, coordination environments, and macrocyclic components curb redox behavior and facilitate reversible molecular switching. By integrating insights from both metal‐containing and metal‐free systems, we outline strategies for developing responsive catenane architectures with potential applications in molecular electronics, sensors, and nanomechanical devices.

链烷是一类有趣的机械互锁分子（mim），由于其动态氧化还原响应行为和独特的拓扑结构而引起了广泛的关注。这些系统的联锁特性允许在电化学刺激下精确控制分子运动，这在设计分子机器和设备方面是有价值的。这篇综述强调了当代在结构修饰以微调其氧化还原性能方面的进展。重点放在取代模式、配位环境和大环组分的变化如何抑制氧化还原行为和促进可逆分子开关。通过整合含金属和无金属系统的见解，我们概述了在分子电子学、传感器和纳米机械设备中开发具有潜在应用前景的响应式链烷体系结构的策略。

引用次数: 0

Late‐Stage Conversion of Terminal Alkynes to Nitriles in Nucleoside Scaffolds: A Tool for Diversification 核苷支架末端炔向腈的后期转化：一种多样化的工具

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.70235

Yun A Yum , Vikas R. Aswar , Vidyasagar Gaikwad , Sushil K. Tripathi , Dnyandev B. Jarhad , Prof. Dr. Lak Shin Jeong

The small nucleoside molecule LJ‐4827 exhibited potent kinase inhibition and in vitro anticancer activity. Driven by bio‐isosteric principles, we synthesized LJ‐5157, which also demonstrated high kinase selectivity and anticancer efficacy. To further expand the structural diversity of bioactive nucleoside analogs, we developed a metal‐free, late‐stage strategy for converting terminal alkynes to nitriles using tert‐butyl nitrite (^tBuONO). By substituting 2‐picoline N‐oxide with N‐methylmorpholine N‐oxide (NMO) as the oxidant, we accomplished efficient nitrile formation in nucleoside scaffolds. This approach broadens the scope of alkyne cleavage chemistry and offers a practical route for analog diversification.

小核苷分子LJ‐4827表现出有效的激酶抑制和体外抗癌活性。在生物等构原理的驱动下，我们合成了LJ‐5157，也显示出高激酶选择性和抗癌功效。为了进一步扩大生物活性核苷类似物的结构多样性，我们开发了一种不含金属的后期策略，利用亚硝酸盐叔丁基（tBuONO）将末端炔转化为腈。通过用N -甲基morpholine N - oxide （NMO）代替2 - picoline N - oxide作为氧化剂，我们在核苷支架中实现了高效的腈生成。这种方法拓宽了炔解理化学的范围，为模拟物多样化提供了一条实用的途径。

引用次数: 0

DMF‐Promoted S─Si Bond Activation Leading to Efficient Activator‐ and Catalyst‐Free C‐S Couplings of Thiosilanes and Organohalides DMF促进S - Si键活化导致硫代硅烷和有机卤化物的高效活化剂和无催化剂C - S偶联

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.202500410

Guoshun Jin , Mengli Li , Xiaohui Li , Yaqi Yang , Prof. Dr. Qing Xu , Prof. Dr. Li‐Biao Han

It was unexpectedly found that, if performed in amide type solvents such as DMF, nucleophilic substitution reaction of heteroaryl halides and thiosilanes could proceed effectively without any activator or catalyst. Mechanistic studies and literature findings implied that a DMF‐promoted direct S─Si bond activation of thiosilanes is most likely the driving force to promote the reaction. This protocol could be extended to alkyl halides and some electron‐deficient aryl halides, showing relatively broad scope of the substrates. This method may be a more convenient and practical way for preparing several types of unsymmetrical thioethers.

出人意料地发现，如果在DMF等酰胺型溶剂中进行，杂芳基卤化物和硫代硅烷的亲核取代反应可以在没有任何活化剂或催化剂的情况下有效地进行。机理研究和文献发现表明，DMF促进硫代硅烷的直接S─Si键活化很可能是促进反应的驱动力。该方案可以推广到烷基卤化物和一些缺乏电子的芳基卤化物，显示出相对广泛的底物范围。该方法可能是制备几种不对称硫醚的更方便和实用的方法。

引用次数: 0

Iron‐Catalyzed Direct C(sp3)–H Sulfonylmethylation of Benzofused Ketones with DMA as a Methylene Source 以DMA为亚甲基源，铁催化苯并酮直接C(sp3) -H磺基甲基化

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.70240

Saiwen Liu , Hong Xiao , Zhihong Yin

An efficient iron‐catalyzed C─H bond functionalization strategy has been developed for the direct sulfonylmethylation of benzofused ketones. This three‐component reaction employs sodium sulfinates as the sulfonyl source and dimethylacetamide (DMA) as a versatile one‐carbon synthon, enabling concurrent construction of C─C and C─S bonds. The protocol demonstrates broad functional group tolerance and proceeds under oxidative conditions using FeCl₃ and K₂S₂O₈. A variety of α‐tetralones, 1‐indanones, and related substrates were transformed into the corresponding α‐sulfonylmethylated derivatives in moderate to good yields. Mechanistic studies suggest a radical pathway involving a key 2‐methylidenecycloalkan‐1‐one intermediate, offering a practical and step‐economical route to sulfone‐containing scaffolds.

建立了一种高效的铁催化C─H键功能化策略，用于苯并酮的直接磺基甲基化。该三组分反应采用亚硫酸钠作为磺酰源，二甲乙酰胺（DMA）作为多用途的一碳合成物，可以同时构建C─C和C─S键。该方案具有广泛的官能团耐受性，并在使用FeCl3和K2S2O₈的氧化条件下进行。多种α‐四酮、1‐吲哚酮和相关底物转化为相应的α‐磺酰基甲基化衍生物，产量中等至较高。机制研究表明，自由基途径涉及关键的2 -甲基环alkan - 1 - 1中间体，为含砜支架提供了一条实用且经济的途径。

引用次数: 0

Recent Synthetic Transformation of 1,1‐Dibromoalk‐1‐enes 1,1‐二溴茂烷‐1‐烯的合成转化研究进展

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.70259

Yun‐Xin Wu , Zhou Sun , Shao‐Wei Bian , Ya‐Ping Han , Gang‐Liu , Yong‐Min Liang

1,1‐Dibromoalk‐1‐enes are a pivotal class of organic synthons and occupy an outstandingly important role in both academic and industrial communities due to their accessibility and commercial availability. The development of novel, powerful, and highly efficient strategy that employed those cost‐effective reagents for the selective assembly of a great deal of structurally diverse elaborated molecular architectures has attracted considerable interest in organic synthesis, medicinal chemistry, and materials science. Over the past few decades, a resurgence of interest regarding 1,1‐dibromoalk‐1‐enes has been witnessed, and substantial research efforts have been dedicated to investigating their reactivity and synthetic applications, with primary focus on developing efficient methodologies for constructing structurally diverse heterocyclic frameworks. In this regard, numerous reaction strategies featuring high reactivity, operational simplicity, and excellent atom economy have been systematically explored, thereby expanding the synthetic utility of 1,1‐dibromoalk‐1‐enes in modern organic chemistry. This review summarizes the development of 1,1‐dibromoalk‐1‐enes through different types of reactions, which could be classified into the following categories: (1) 1,1‐dibromoalk‐1‐ene as alkenylation reagent; (2) 1,1‐dibromoalk‐1‐ene as alkynylation reagent; (3) cyclization reaction of 1,1‐dibromoalk‐1‐enes; and (4) other types of reactions of 1,1‐dibromoalk‐1‐ene.

1,1‐二溴烷‐1‐烯是一类关键的有机合成子，由于其可及性和商业可行性，在学术界和工业界都占有非常重要的地位。利用这些具有成本效益的试剂对大量结构多样的精细分子结构进行选择性组装，这种新颖、强大、高效的策略的发展已经引起了有机合成、药物化学和材料科学领域的极大兴趣。在过去的几十年里，人们对1,1‐二溴链烷‐1‐烯的兴趣重新燃起，大量的研究工作致力于研究它们的反应性和合成应用，主要集中在开发构建结构多样的杂环框架的有效方法上。在这方面，人们系统地探索了许多具有高反应活性、操作简单和极好的原子经济性的反应策略，从而扩大了1,1‐二溴茂烷‐1‐烯在现代有机化学中的合成用途。本文综述了1,1‐二溴化烯在不同类型反应中的发展，可分为以下几类：(1)作为烯化试剂的1,1‐二溴化烯；(2) 1,1‐二溴化烷‐1‐烯作为烷基化试剂；(3) 1,1‐二溴茂烷‐1‐烯的环化反应；(4) 1,1‐二溴化烷‐1‐烯的其他类型的反应。

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引用次数: 0

DFT Study on the Role of Lewis Acids in Benzoxasilole Synthesis Via Intramolecular Hosomi–Sakurai Reaction 路易斯酸在分子内Hosomi-Sakurai反应合成苯并恶唑中的作用的DFT研究

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.202500571

Carlos Rodríguez‐Arias , Abel Cózar

The reaction mechanism of the Lewis acid–catalyzed intramolecular Hosomi–Sakurai reaction of o–allylsilyl benzaldehyde has been analyzed computationally. Our calculations indicate that the reaction follows a stepwise mechanism, in which the initial formation of a bicyclic nonclassical cation after the first C─C bond formation is followed by a conformational rearrangement of the bicyclic intermediate generated and a concomitant Si─C cleavage and Si─O bond formation, ultimately yielding the final benzoxasilole. The analysis of the relationship between the energetic profile and Lewis acid structure shows that the first C─C bond formation process and the stability/reactivity of these bicyclic nonclassical cationic intermediates determine its catalytic activity.

对Lewis酸催化邻丙烯基硅基苯甲醛分子内Hosomi-Sakurai反应机理进行了计算分析。我们的计算表明，反应遵循一个循序渐进的机制，其中，在第一个C─C键形成后，双环非经典阳离子的初始形成，随后产生的双环中间体的构象重排，伴随的Si─C裂解和Si─O键形成，最终产生最终的苯并西林。对能态分布与Lewis酸结构的关系分析表明，这些双环非经典阳离子中间体的第一次C─C键形成过程和稳定性/反应性决定了其催化活性。

引用次数: 0

Metal‐Free Organophotocatalyzed Trifluoroethylation/Esterification of Alkenes 无金属有机光催化烯烃的三氟乙化/酯化反应

IF 2.7 4区化学 Q1 CHEMISTRY, ORGANIC

Asian Journal of Organic Chemistry

Pub Date : 2025-12-01 DOI: 10.1002/ajoc.70232

Can Zeng , Xiangqing Zhang , Yue Wang , Yao‐Fu Zeng , Fang Han

A metal‐free, organophotocatalyzed three‐component reaction between alkenes, 2,2,2‐trifluoroiodoethane, and carboxylic acids was developed. This protocol simultaneously introduces a trifluoroethyl group and an ester moiety in a single step. Preliminary mechanistic studies suggest the reaction proceeds via a radical pathway.

研究了烯烃、2,2,2 -三氟碘乙烷和羧酸之间无金属、有机光催化的三组分反应。该方法在一步中同时引入一个三氟乙基和一个酯段。初步的机理研究表明，反应是通过自由基途径进行的。

引用次数: 0

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