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One-Pot Functionalization at C-2,2′-Oxidation and C-3,3′-Bromination of 3,3′-Bis-7-Azaindolylmethane Using NBS/CAN as a Reagent: Synthesis of Brominated 3,3′-Bis-7-Aza-2-indalones 以NBS/CAN为试剂的3,3 ' -双-7-氮杂吲哚甲烷c -2,2 ' -氧化和c -3,3 ' -溴化的一锅官能化合成3,3 ' -双-7-氮杂吲哚酮
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-07 DOI: 10.1002/ajoc.70247
Pavithra Elavarasan, Sathananthan Kannadasan, Ponnusamy Shanmugam

The first study of the NBS/ceric (IV) ammonium nitrate (CAN) has emerged as a powerful and efficient reagent for the difunctionalization at C-2,2′-oxidation and C-3,3′-bromination of 3,3′-bis-7-azaindolyl methane to form isolable diastereomers of polybrominated 7-aza-bis-2-indalones as established by 1H NMR study. The scope of the reaction, characterization of products including XRD technique, and a plausible mechanism for the formation of products are described. Synthetic use of one of the products thus obtained, namely 3′-methylene bis (3,5-dibromo-1-methyl-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one), has been demonstrated by the synthesis of a functionally diverse dispiro[pyrrolo[2,3-b]pyridine-3,1′-cycloheptane derivative by a sequence of reactions (1) zinc/AcOH reduction, (2) allylation, and (3) RCM reaction using Grubbs-II catalyst.

NBS/ceric (IV)硝酸铵(CAN)的首次研究表明,它是一种强大而有效的试剂,可用于3,3 ' -双-7-氮杂酰基甲烷的c -2,2 ' -氧化和c -3,3 ' -溴化,形成可分离的多溴化7-氮杂-双-2-吲哚酮的非对映体。叙述了反应的范围、产物的表征(包括XRD技术)和产物形成的合理机理。通过一系列反应(1)锌/AcOH还原,(2)烯丙基化,(3)grbbs - ii催化剂RCM反应,合成了功能多样化的吡咯[2,3-b]吡啶-3,1 ' -环庚烷衍生物,证明了3 ' -亚甲基双(3,5-二溴-1-甲基-1,3-二氢- 2h -吡咯[2,3-b]吡啶-3,1 ' -环庚烷衍生物的合成用途。
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引用次数: 0
Metal-Free and Selective Synthesis of Benzo[d]Isothiazol-3(2H)-Ones and Corresponding 1-Oxides 苯并[d]异噻唑- 3(2H) -酮及其1 -氧化物的无金属选择性合成
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-05 DOI: 10.1002/ajoc.70241
Yongli He, Yong Huang, Ke Yang, Bindong Li

Metal-free and selective synthesis of benzo[d]isothiazol-3(2H)-ones and corresponding 1-oxides has been developed. The use of NCS enables the formation of a diverse range of benzo[d]isothiazol-3(2H)-ones from 2-mercaptobenzamides in excellent yields. Furthermore, this protocol achieves cascade synthesis of the corresponding 1-oxides by employing excess amounts of NCS or Selectfluor, which facilitates N─S bond formation followed by S═O bond generation. Additionally, mechanistic studies indicate that this strategy may involve disulfide intermediates. Notably, this approach offers a complementary method for accessing both benzo[d]isothiazol-3(2H)-ones and their corresponding 1-oxides.

研究了苯并[d]异噻唑- 3(2H) -酮及其相应的1 -氧化物的无金属选择性合成。NCS的使用使2 -巯基苯甲酰胺以优异的收率形成多种苯并[d]异噻唑- 3(2H) -酮。此外,该方案通过使用过量的NCS或Selectfluor实现了相应的1‐氧化物的级联合成,这促进了N─S键的形成,然后是S = O键的生成。此外,机理研究表明,这一策略可能涉及二硫化物中间体。值得注意的是,该方法为获得苯并[d]异噻唑- 3(2H) -酮及其相应的1 -氧化物提供了一种补充方法。
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引用次数: 0
Rh(II)‐Catalyzed Single‐Carbon‐Atom Skeletal Editing of Pyrazolidinones with Diazoindolinones for the Synthesis of 3‐Spirooxindoles Rh(II)催化吡唑烷酮与重氮吲哚酮的单碳原子骨架编辑合成3-螺旋吲哚
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500454
Meng Chen , Yingzhi Peng , Danhong Hu
The 3‐spirooxindole scaffolds play important roles in medical and biological research of many marketed drugs and natural products. In this study, we report the single‐carbon‐atom skeletal editing of pyrazolidinones by employing a Rh(II)‐catalyzed one‐carbon insertion and [5 + 1] ring expansion strategy with diazoindolinones as the carbene precursors, providing a series of 5“,6”‐dihydro spiro[indoline‐3,2“‐pyrimidine]‐2,4”‐diones. This protocol exhibits a broad functional group tolerance, mild reaction conditions, simple operation, and excellent atom economy. Moreover, diazoindolinones are demonstrated to be able to edit N─N bond and provide N‐heterocycle 3‐spirooxindole derivatives, which have a dinitrogen substituted quaternary carbon center, broadening their synthetic application prospects.
3-螺霉哚支架在许多已上市药物和天然产物的医学和生物学研究中发挥着重要作用。在这项研究中,我们报道了采用Rh(II)催化的单碳插入和[5 + 1]环扩张策略,以二氮吲哚酮为碳前体,对吡唑烷酮进行单碳原子骨架编辑,得到了一系列5 ',6 ' -二氢螺旋[吲哚-3,2 ' -嘧啶]-2,4 ' -二酮。该工艺具有官能团耐受性广、反应条件温和、操作简单、原子经济性好等特点。此外,重氮吲哚酮类化合物能够编辑N─N键,并提供具有二氮取代的季碳中心的N-杂环3-螺环吲哚衍生物,拓宽了它们的合成应用前景。
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引用次数: 0
Highly Stereoselective Gem‐Dimethylcyclopropanation of Allylic Alcohols Promoted by Alkylidene Titanocenes 钛茂烯烷基基促进烯丙醇的高立体选择性gem -二甲基环丙化反应
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500606
José Manuel Botubol‐Ares , Natalia Castillo‐Ruiz , Isidro G. Collado , María Jesús Durán‐Peña , Rosario Hernández‐Galán
A novel methodology for the direct gem‐dimethylcyclopropanation of a series of acyclic and cyclic primary and secondary allylic alcohols is herein described. The reaction proceeds in a regio‐, chemo‐, and stereoselective manner, affording the corresponding gem‐dimethylcyclopropane derivatives in moderate yields. We postulate that an alkylidene titanocene, generated in situ from sub‐stoichiometric amounts of low‐valent titanium species, Mg and 2,2‐dichloropropane under mild reaction conditions, serves as the active species. The scope, limitations and a plausible mechanism of this metal‐promoted transformation are also presented.
本文描述了一种新的方法,用于一系列无环和环伯和仲烯丙基醇的直接双甲基环丙烷化。该反应以区域选择性、化学选择性和立体选择性的方式进行,以中等产率生成相应的宝石-二甲基环丙烷衍生物。我们假设,在温和的反应条件下,由亚化学计量量的低价钛、Mg和2,2-二氯丙烷原位生成的烷基二茂钛作为活性物质。本文还介绍了这种金属促进相变的范围、局限性和可能的机理。
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引用次数: 0
Pd/Ag‐Catalyzed Cascade Reaction of Alkynol Homocoupling: Access to Symmetrical Ethers 钯/银催化的烷基醇均偶联级联反应:获得对称醚
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.70203
Dipak B. Deokar , Vaijayanthi Kshir Sagar , Y. Bhargav Kumar , Yarasi Soujanya , Balasubramanian Sridhar , Pravin R. Likhar
We present a convenient one‐pot synthesis of ethers using alkynols as the sole starting material. This method yields various ether derivatives through a Pd/Ag catalytic system, achieving good to excellent yields. The reaction occurs silver‐coordinated intermediate of 4‐hydroxy‐1‐arylbutan‐1‐one, ultimately leading to the formation of symmetrical ethers. This approach emphasizes the synergistic effect of Pd/Ag‐catalyzed transformations in producing symmetrical ether products. The detailed reaction mechanism was thoroughly investigated using density functional theory studies.
我们提出了一种方便的以烷基醇为唯一起始原料的一锅合成醚的方法。该方法通过钯/银催化体系生成各种醚衍生物,获得良好至优异的收率。反应发生在4-羟基-1-芳基丁烷-1- 1的银配位中间体上,最终生成对称醚。这种方法强调了钯/银催化转化在产生对称醚产物中的协同效应。利用密度泛函理论对反应机理进行了深入研究。
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引用次数: 0
Synthesis of Hydroxynitriles by N,N‐Dimethylformamide‐Stabilized Ruthenium Nanoparticles‐Catalyzed α‐Alkylation of Arylacetonitriles with Diols N,N-二甲基甲酰胺稳定钌纳米颗粒合成羟基腈-催化芳基乙腈与二醇的α-烷基化反应
IF 2.7 4区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-11-01 DOI: 10.1002/ajoc.202500610
Nobuki Katayama , Akihiro Marutani , Masatoshi Safumi , Keiko Uchida , Prof. Dr. Takeyuki Suzuki , Prof. Dr. Yasushi Obora
To efficiently synthesize hydroxynitriles, arylacetonitriles were selectively α‐monoalkylated with diols, catalyzed using N,N‐dimethylformamide‐stabilized ruthenium nanoparticles (NPs). The Ru NPs were stable in air and moisture and possessed high catalytic activity and selectivity, even at loadings as low as 0.3 mol%, without requiring the use of strong bases. The results of the control experiments suggested that excess diol enhanced the Ru NPs’ catalytic activity and that the reaction mechanism involved dehydrogenation, condensation, and hydrogenation pathways.
为了高效合成羟基腈,采用N,N-二甲基甲酰胺稳定钌纳米颗粒(NPs)催化芳基乙腈与二醇选择性α-单烷基化。钌NPs在空气和水分中稳定,具有高的催化活性和选择性,即使在低至0.3 mol%的负载下,也不需要使用强碱。对照实验结果表明,过量的二醇增强了Ru NPs的催化活性,反应机制包括脱氢、缩合和加氢三种途径。
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引用次数: 0
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
期刊
Asian Journal of Organic Chemistry
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