Pub Date : 2025-12-08DOI: 10.1016/j.tet.2025.135089
Rajaghatta N. Suresh , Toreshettahally R. Swaroop , Kanchugarakoppal S. Rangappa
Copper-catalyzed/mediated synthesis of heterocycles plays a crucial role in the field of medicinal chemistry as well as synthetic organic chemistry. Notably, copper salts facilitate the C-S bond formation during the synthesis of heterocycles. On the other hand, they also serve as oxidizing agents, metal catalysts and Lewis acids. This review summarizes an updated collection of copper-catalyzed/mediated synthesis of thiophenes and benzothiophenes. Furthermore, optimal reaction conditions, reaction's scope/generality, pros and/or cons, discussion of control experiments and plausible mechanisms of the reactions are presented. In addition, this review article collects important strategies of copper-catalyzed/mediated synthesis of thiophenes and benzothiophenes reported from 2010 to 2024, which is advantageous for many chemists interested in transition metal-catalyzed reactions.
{"title":"Copper-catalyzed/mediated synthesis of thiophenes and benzothiophenes: an updated review","authors":"Rajaghatta N. Suresh , Toreshettahally R. Swaroop , Kanchugarakoppal S. Rangappa","doi":"10.1016/j.tet.2025.135089","DOIUrl":"10.1016/j.tet.2025.135089","url":null,"abstract":"<div><div>Copper-catalyzed/mediated synthesis of heterocycles plays a crucial role in the field of medicinal chemistry as well as synthetic organic chemistry. Notably, copper salts facilitate the C-S bond formation during the synthesis of heterocycles. On the other hand, they also serve as oxidizing agents, metal catalysts and Lewis acids. This review summarizes an updated collection of copper-catalyzed/mediated synthesis of thiophenes and benzothiophenes. Furthermore, optimal reaction conditions, reaction's scope/generality, pros and/or cons, discussion of control experiments and plausible mechanisms of the reactions are presented. In addition, this review article collects important strategies of copper-catalyzed/mediated synthesis of thiophenes and benzothiophenes reported from 2010 to 2024, which is advantageous for many chemists interested in transition metal-catalyzed reactions.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135089"},"PeriodicalIF":2.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-02DOI: 10.1016/j.tet.2025.135067
Qing Shen , Shuangqiao Li , Xianglin Zhong , Yang-Bao Miao , Jiahong Li
This study developed a novel photocatalyst-free, visible-light-driven strategy for the synthesis of diaryl ethers. Utilizing 455 nm blue light to excite nitroarenes and enhance their electrophilicity, the method efficiently constructs C–O bonds via an SNAr reaction between nitroarenes and phenolic compounds under mild alkaline conditions. This approach eliminates the need for transition metals, operates at room temperature under mild conditions, exhibits broad substrate scope, and offers simple operation, thereby providing a green and efficient new pathway for diaryl ether synthesis.
{"title":"Visible-light-promoted synthesis of diaryl ethers from nitroarenes and phenols","authors":"Qing Shen , Shuangqiao Li , Xianglin Zhong , Yang-Bao Miao , Jiahong Li","doi":"10.1016/j.tet.2025.135067","DOIUrl":"10.1016/j.tet.2025.135067","url":null,"abstract":"<div><div>This study developed a novel photocatalyst-free, visible-light-driven strategy for the synthesis of diaryl ethers. Utilizing 455 nm blue light to excite nitroarenes and enhance their electrophilicity, the method efficiently constructs C–O bonds via an SNAr reaction between nitroarenes and phenolic compounds under mild alkaline conditions. This approach eliminates the need for transition metals, operates at room temperature under mild conditions, exhibits broad substrate scope, and offers simple operation, thereby providing a green and efficient new pathway for diaryl ether synthesis.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135067"},"PeriodicalIF":2.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-02DOI: 10.1016/j.tet.2025.135074
Laiba Anwar , Sajjad Ahmad , Kulsoom Ghulam Ali , Bushra Parveen , Ameer Fawad Zahoor , Syed Ali Raza Naqvi , Jaweriya Ashraf , Usman Nazeer
The Stille coupling reaction has garnered significant interest as an innovative approach for forming carbon-carbon bonds due to its broad substrate scope and the stability of organotin compounds. Traditionally reliant on palladium-based homogeneous catalysis, recent developments have explored heterogeneous catalytic systems that utilize transition metals and their nanoparticles to enhance sustainability, cost-effectiveness and ease of recovery. Metal-based nanoparticles (Pd, Au and Cu) with high surface-to-volume ratio and excellent catalytic activity offer various advantages including enhanced thermal stability, reduced metal leaching, facile catalyst recovery and reusability in heterogeneous catalysis. The Stille reaction has also been extensively employed in the synthesis of natural products. This review summarizes the recent advancements in metallic systems and their nanoparticles-mediated Stille coupling reactions covering literature from 2015 to 2025. Moreover, relevant reaction mechanisms and applications have also been discussed.
{"title":"Recent synthetic innovations in Stille coupling reaction: A review","authors":"Laiba Anwar , Sajjad Ahmad , Kulsoom Ghulam Ali , Bushra Parveen , Ameer Fawad Zahoor , Syed Ali Raza Naqvi , Jaweriya Ashraf , Usman Nazeer","doi":"10.1016/j.tet.2025.135074","DOIUrl":"10.1016/j.tet.2025.135074","url":null,"abstract":"<div><div>The Stille coupling reaction has garnered significant interest as an innovative approach for forming carbon-carbon bonds due to its broad substrate scope and the stability of organotin compounds. Traditionally reliant on palladium-based homogeneous catalysis, recent developments have explored heterogeneous catalytic systems that utilize transition metals and their nanoparticles to enhance sustainability, cost-effectiveness and ease of recovery. Metal-based nanoparticles (Pd, Au and Cu) with high surface-to-volume ratio and excellent catalytic activity offer various advantages including enhanced thermal stability, reduced metal leaching, facile catalyst recovery and reusability in heterogeneous catalysis. The Stille reaction has also been extensively employed in the synthesis of natural products. This review summarizes the recent advancements in metallic systems and their nanoparticles-mediated Stille coupling reactions covering literature from 2015 to 2025. Moreover, relevant reaction mechanisms and applications have also been discussed.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135074"},"PeriodicalIF":2.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01DOI: 10.1016/j.tet.2025.135086
Upma Gulati , Anjali Gupta, Joydev K. Laha
A classical transformation involving benzylic oxidation is developed using a metal-free approach. Unlike the reported methods, this report unveils for the first time the synthesis of arylglyoxylic esters from arylacetic esters utilizing the TBN/NHS catalytic system. A variety of substrates in moderate to good yields (up to 85 %) are synthesized to exhibit the practical applicability of the reaction. The synthesized products display great utility and value in terms of synthetic transformations including the synthesis of many useful scaffolds. Mechanistic studies reveal the formation of a benzylic functionalized nitro compound as active intermediate leading to the formation of desired product.
{"title":"Tuning the reactivity of benzylic radicals by virtue of the presence of an acid/ester functional group at the benzylic carbon","authors":"Upma Gulati , Anjali Gupta, Joydev K. Laha","doi":"10.1016/j.tet.2025.135086","DOIUrl":"10.1016/j.tet.2025.135086","url":null,"abstract":"<div><div>A classical transformation involving benzylic oxidation is developed using a metal-free approach. Unlike the reported methods, this report unveils for the first time the synthesis of arylglyoxylic esters from arylacetic esters utilizing the TBN/NHS catalytic system. A variety of substrates in moderate to good yields (up to 85 %) are synthesized to exhibit the practical applicability of the reaction. The synthesized products display great utility and value in terms of synthetic transformations including the synthesis of many useful scaffolds. Mechanistic studies reveal the formation of a benzylic functionalized nitro compound as active intermediate leading to the formation of desired product.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135086"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01DOI: 10.1016/j.tet.2025.135085
Irina Yu. Krasnova, Nina V. Kuchkina, Elena S. Chamkina, Dmitry Yu. Antonov, Alexandr A. Chamkin, Zinaida B. Shifrina
A series of ferrocenyl-functionalized dendrons were synthesized as model precursors for redox-active Janus dendrimers with rigid rylene chromophore cores. Azidoferrocenes incorporating methylene, hexyl, or undecyl spacers were obtained via acylation–reduction–azidation sequences and subsequently conjugated to phenylene-based ethynyl dendrons through Cu(I)-catalyzed azide–alkyne cycloaddition, affording dendritic architectures with high structural definition. Comprehensive characterization by NMR spectroscopy and MALDI-ToF mass spectrometry confirmed the successful incorporation of ferrocenyl termini. Cyclic voltammetry revealed a single, chemically reversible one-electron oxidation wave for all compounds, consistent with non-interacting ferrocenyl sites. For dendrons bearing extended alkyl linkers (7, 7 N, 8, 8 N), the redox processes were fully reversible and diffusion-controlled, in agreement with efficient intramolecular electron transfer (electron-hopping). In contrast, dendrons with short methylene spacers (6, 6 N) exhibited broadened voltammetric profiles and increased ΔEp at high scan rates, indicative of hindered charge transfer kinetics imposed by proximal triazole groups. Pyridyl substitution had negligible electronic effects but imparted tunable solubility. These findings establish clear structure–redox correlations and provide a robust foundation for the future construction of multifunctional Janus dendrimers integrating ferrocenyl dendrons with rylene-based fluorescent and photothermal cores.
合成了一系列二茂铁功能化的树突，作为具有刚性乙烯发色团核的氧化还原活性Janus树突的模型前体。通过酰化-还原-叠氮化序列得到含有亚甲基、己基或十一基间隔物的叠氮二茂化合物，随后通过Cu(I)催化叠氮-炔环加成与苯基乙基树突结合，形成具有高结构清晰度的树突结构。通过核磁共振光谱和MALDI-ToF质谱综合表征证实了二茂铁末端的成功结合。循环伏安法显示，所有化合物都有一个化学可逆的单电子氧化波，与非相互作用的二茂铁基位点一致。对于含有扩展烷基连接体（7,7 N, 8,8 N）的树突，氧化还原过程是完全可逆和扩散控制的，与有效的分子内电子转移（电子跳迁）一致。相比之下，具有短亚甲基间隔物（6,6 N）的树突在高扫描速率下表现出宽的伏安谱和增加的ΔEp，表明近端三唑基团施加的电荷转移动力学受到阻碍。吡啶基取代的电子效应可以忽略不计，但其溶解度可调。这些发现建立了清晰的结构-氧化还原相关性，并为未来构建将二茂铁树突与乙烯基荧光和光热核结合的多功能Janus树突提供了坚实的基础。
{"title":"Ferrocene terminated aromatic dendrons for the construction of Janus dendrimers. Synthesis and electrochemical study","authors":"Irina Yu. Krasnova, Nina V. Kuchkina, Elena S. Chamkina, Dmitry Yu. Antonov, Alexandr A. Chamkin, Zinaida B. Shifrina","doi":"10.1016/j.tet.2025.135085","DOIUrl":"10.1016/j.tet.2025.135085","url":null,"abstract":"<div><div>A series of ferrocenyl-functionalized dendrons were synthesized as model precursors for redox-active Janus dendrimers with rigid rylene chromophore cores. Azidoferrocenes incorporating methylene, hexyl, or undecyl spacers were obtained via acylation–reduction–azidation sequences and subsequently conjugated to phenylene-based ethynyl dendrons through Cu(I)-catalyzed azide–alkyne cycloaddition, affording dendritic architectures with high structural definition. Comprehensive characterization by NMR spectroscopy and MALDI-ToF mass spectrometry confirmed the successful incorporation of ferrocenyl termini. Cyclic voltammetry revealed a single, chemically reversible one-electron oxidation wave for all compounds, consistent with non-interacting ferrocenyl sites. For dendrons bearing extended alkyl linkers (7, 7 N, 8, 8 N), the redox processes were fully reversible and diffusion-controlled, in agreement with efficient intramolecular electron transfer (electron-hopping). In contrast, dendrons with short methylene spacers (6, 6 N) exhibited broadened voltammetric profiles and increased ΔEp at high scan rates, indicative of hindered charge transfer kinetics imposed by proximal triazole groups. Pyridyl substitution had negligible electronic effects but imparted tunable solubility. These findings establish clear structure–redox correlations and provide a robust foundation for the future construction of multifunctional Janus dendrimers integrating ferrocenyl dendrons with rylene-based fluorescent and photothermal cores.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135085"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-29DOI: 10.1016/j.tet.2025.135073
Hao Lan , Lei Ding , Yuhan Wang , Yunfei Li , Yu Lin , Weizhi Sun , Long Jiang , Chao Xu
Riboflavin 2′,3′,4′,5′-tetraacetate (RFTA) is a classic enzyme-mimetic photocatalyst that has demonstrated excellent catalytic performance in various oxidation reactions. In this study, we found that RFTA, in the presence of visible light and oxygen, can promote the cleavage of C(sp3)-N bonds and achieve one-pot oxidative amidation to construct 3,4-dihydroisoquinolin-1(2H)-one, a heterocyclic core widely present in many bioactive molecules, with a yield of 72 %. The reaction proceeds smoothly at room temperature and atmospheric pressure under 520 nm light irradiation using N-benzyl-1,2,3,4-tetrahydroisoquinoline as the substrate, without the need for precious metals, stoichiometric oxidants, or added bases, and is operationally simple. Preliminary mechanistic studies suggest that the reaction may first undergo single-electron transfer (SET), followed by a light-induced proton-coupled electron transfer (PCET) process, which cooperatively achieves the selective cleavage of the C(sp3)-N bond and the site-specific oxidation of the C(sp3)-H bond, thereby obtaining high chemical selectivity. Although this method still has certain limitations, we hope that this initial exploration can provide a useful supplement to the application of RFTA in biomimetic photocatalysis and offer a mild and practical new strategy for the synthesis of dihydroisoquinolinone skeletons with drug value.
{"title":"Green-light/oxygen cooperative RFTA catalysis: One-pot debenzylation-acylation of N-benzyltetrahydroisoquinolines to access 3,4-dihydroisoquinolin-1(2H)-one","authors":"Hao Lan , Lei Ding , Yuhan Wang , Yunfei Li , Yu Lin , Weizhi Sun , Long Jiang , Chao Xu","doi":"10.1016/j.tet.2025.135073","DOIUrl":"10.1016/j.tet.2025.135073","url":null,"abstract":"<div><div>Riboflavin 2′,3′,4′,5′-tetraacetate (RFTA) is a classic enzyme-mimetic photocatalyst that has demonstrated excellent catalytic performance in various oxidation reactions. In this study, we found that RFTA, in the presence of visible light and oxygen, can promote the cleavage of C(sp<sup>3</sup>)-N bonds and achieve one-pot oxidative amidation to construct 3,4-dihydroisoquinolin-1(2H)-one, a heterocyclic core widely present in many bioactive molecules, with a yield of 72 %. The reaction proceeds smoothly at room temperature and atmospheric pressure under 520 nm light irradiation using N-benzyl-1,2,3,4-tetrahydroisoquinoline as the substrate, without the need for precious metals, stoichiometric oxidants, or added bases, and is operationally simple. Preliminary mechanistic studies suggest that the reaction may first undergo single-electron transfer (SET), followed by a light-induced proton-coupled electron transfer (PCET) process, which cooperatively achieves the selective cleavage of the C(sp<sup>3</sup>)-N bond and the site-specific oxidation of the C(sp<sup>3</sup>)-H bond, thereby obtaining high chemical selectivity. Although this method still has certain limitations, we hope that this initial exploration can provide a useful supplement to the application of RFTA in biomimetic photocatalysis and offer a mild and practical new strategy for the synthesis of dihydroisoquinolinone skeletons with drug value.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135073"},"PeriodicalIF":2.2,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-28DOI: 10.1016/j.tet.2025.135072
Kai-Kai Wang , Qing Xu , Xia-Shi Gao , Liang-Man Wu , Yue-Yao Ma , Li-Fang Yang , Rongxiang Chen
In this study, we describe a domino reaction involving acyclic α,β-unsaturated imines as C2 synthon with α-bromomalonate, leading to the formation of polysubstituted cyclopropanes via a Michael-initiated ring-closure/cyclopropanation sequence under mild conditions. This approach enables the synthesis of a diverse array of cyclopropanes bearing two adjacent tertiary stereogenic centers, achieving high yields (up to 98 %) with excellent chemo-, regio-, and diastereoselectivities (all cases >25:1 dr). Furthermore, the synthetic utility of this methodology is demonstrated through late-stage functionalization and the modification of drug-like molecules, underscoring its potential in complex molecule synthesis. The structure of a representative product was unambiguously confirmed by X-ray crystallography.
{"title":"Synthesis of polysubstituted cyclopropanes via [2 + 1] cycloaddition reaction of acyclic α,β-unsaturated imines with α-bromomalonate","authors":"Kai-Kai Wang , Qing Xu , Xia-Shi Gao , Liang-Man Wu , Yue-Yao Ma , Li-Fang Yang , Rongxiang Chen","doi":"10.1016/j.tet.2025.135072","DOIUrl":"10.1016/j.tet.2025.135072","url":null,"abstract":"<div><div>In this study, we describe a domino reaction involving acyclic α,β-unsaturated imines as C2 synthon with α-bromomalonate, leading to the formation of polysubstituted cyclopropanes via a Michael-initiated ring-closure/cyclopropanation sequence under mild conditions. This approach enables the synthesis of a diverse array of cyclopropanes bearing two adjacent tertiary stereogenic centers, achieving high yields (up to 98 %) with excellent chemo-, regio-, and diastereoselectivities (all cases >25:1 dr). Furthermore, the synthetic utility of this methodology is demonstrated through late-stage functionalization and the modification of drug-like molecules, underscoring its potential in complex molecule synthesis. The structure of a representative product was unambiguously confirmed by X-ray crystallography.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135072"},"PeriodicalIF":2.2,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-26DOI: 10.1016/j.tet.2025.135071
Tongyue Wu , Zhuoran Sun , Yuxin Cheng , Xu Zhu , Zhi Li , Yongheng Shi , Jingli Liu , Hui Guo , Hao Yan
Deep eutectic solvents have good biodegradability, low volatility, and efficient reusability. In the present work, deep eutectic solvents were used as solvents and catalysts to promote the cyclization reaction of sulfonylhydrazine compounds with β-dicarbonyl compounds, which is highly efficient and easy to operate. In addition, the post-treatment is simple without complicated post-processing such as column chromatography purification. The new synthesis process has good versatility. It is suitable for industrialized-scale production.
{"title":"A new synthesis process of N-sulfonyl pyrazoles from sulfonyl hydrazines and β-diketones promoted by deep eutectic solvents","authors":"Tongyue Wu , Zhuoran Sun , Yuxin Cheng , Xu Zhu , Zhi Li , Yongheng Shi , Jingli Liu , Hui Guo , Hao Yan","doi":"10.1016/j.tet.2025.135071","DOIUrl":"10.1016/j.tet.2025.135071","url":null,"abstract":"<div><div>Deep eutectic solvents have good biodegradability, low volatility, and efficient reusability. In the present work, deep eutectic solvents were used as solvents and catalysts to promote the cyclization reaction of sulfonylhydrazine compounds with β-dicarbonyl compounds, which is highly efficient and easy to operate. In addition, the post-treatment is simple without complicated post-processing such as column chromatography purification. The new synthesis process has good versatility. It is suitable for industrialized-scale production.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135071"},"PeriodicalIF":2.2,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-25DOI: 10.1016/j.tet.2025.135069
Wenxue Li , Zhenjie Qi , Zhenyu An , Yinjun Wei , Boyue Lin , Wenxin Chen , Yafeng Liu
An efficient electrochemical oxidation cyclization of 2-vinylanilines and isothiocyanates has been achieved for the synthesis of 2-aminoquinolines via NaI-mediated desulfurative cyclization. The protocol is further characterized by its high yield, broad substrate scope, and operational simplicity. Mechanistic studies reveal that the reaction involves the formation of a thiourea intermediate from 2-vinylanilines and isothiocyanates under electrochemical oxidation.
{"title":"Access to 2-aminoquinolines from 2-vinylanilines and isothiocyanates via electrochemically induced desulfurative cyclization","authors":"Wenxue Li , Zhenjie Qi , Zhenyu An , Yinjun Wei , Boyue Lin , Wenxin Chen , Yafeng Liu","doi":"10.1016/j.tet.2025.135069","DOIUrl":"10.1016/j.tet.2025.135069","url":null,"abstract":"<div><div>An efficient electrochemical oxidation cyclization of 2-vinylanilines and isothiocyanates has been achieved for the synthesis of 2-aminoquinolines <em>via</em> NaI-mediated desulfurative cyclization. The protocol is further characterized by its high yield, broad substrate scope, and operational simplicity. Mechanistic studies reveal that the reaction involves the formation of a thiourea intermediate from 2-vinylanilines and isothiocyanates under electrochemical oxidation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135069"},"PeriodicalIF":2.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-24DOI: 10.1016/j.tet.2025.135070
Karishma Tiwari , Garima Pandey
Covalent organic frameworks (COFs) have rapidly emerged as a versatile class of highly crystalline porous polymers with tunable functionalities showing broad applications in the field of gas storage, catalysis, energy storage, sensing, drug delivery, and hydrogen evolution, etc. Fundamental to COF Chemistry is dynamic covalent chemistry (DCC), which allows error corrections during reversible bond formation to produce well-ordered frameworks. Several named reactions governed by DCC have been exploited for COF synthesis. This review provides a critical evaluation of fundamental reversible boronic acid condensation and key named reactions, including highly reversible Schiff base condensation, as well as reactions with low to moderate reversibility or irreversible nature, particularly Knoevenagel condensation, aldol condensation, Horner–Wadsworth–Emmons (HWE) condensation, Suzuki-type cross-coupling, Sonogashira coupling, and the aza-Diels–Alder reaction. Each of these reactions yields COFs with distinct structures and functionalities determined by the extent of their reaction reversibility. COFs synthesized through reversible condensation exhibit high crystallinity but limited stability, whereas frameworks produced by an irreversible approach show enhanced stability at the expense of crystallinity. Moreover, robustness in COFs can be improved by combining reversible and irreversible reactions or through post-synthetic modifications.
{"title":"The named reaction toolbox for COF synthesis: controlling crystallinity, stability, and performance","authors":"Karishma Tiwari , Garima Pandey","doi":"10.1016/j.tet.2025.135070","DOIUrl":"10.1016/j.tet.2025.135070","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) have rapidly emerged as a versatile class of highly crystalline porous polymers with tunable functionalities showing broad applications in the field of gas storage, catalysis, energy storage, sensing, drug delivery, and hydrogen evolution, etc. Fundamental to COF Chemistry is dynamic covalent chemistry (DCC), which allows error corrections during reversible bond formation to produce well-ordered frameworks. Several named reactions governed by DCC have been exploited for COF synthesis. This review provides a critical evaluation of fundamental reversible boronic acid condensation and key named reactions, including highly reversible Schiff base condensation, as well as reactions with low to moderate reversibility or irreversible nature, particularly Knoevenagel condensation, aldol condensation, Horner–Wadsworth–Emmons (HWE) condensation, Suzuki-type cross-coupling, Sonogashira coupling, and the aza-Diels–Alder reaction. Each of these reactions yields COFs with distinct structures and functionalities determined by the extent of their reaction reversibility. COFs synthesized through reversible condensation exhibit high crystallinity but limited stability, whereas frameworks produced by an irreversible approach show enhanced stability at the expense of crystallinity. Moreover, robustness in COFs can be improved by combining reversible and irreversible reactions or through post-synthetic modifications.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135070"},"PeriodicalIF":2.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145622335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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