Pub Date : 2025-10-30DOI: 10.1016/j.tet.2025.135039
Jia-Le Fu , Jia-Lun Luo , Xue-Feng Zhao , Dan Zhang , Tao Wu , Hongwei Si , Peng-Fei Dai
The oxidation of aldehydes to corresponding carboxylic acids catalyzed by tetra-n-butylammonium decatungstate (TBADT) under visible light in CH3CN or H2O have been realized for the first time. Mono-aldehydes and dialdehydes, especially aldehydes bearing with electron-withdrawing groups (e.g.: –NO2, –CO2R, –CHO, –COR, –CN, –CF3, etc.) and vulnerable groups (e.g.: –OH, -SMe, etc.) are well compatible with in moderate to good yields. And detailed mechanistic investigations have revealed the catalytic role of TBADT in the oxidation. A gram-scale synthesis has been implemented with a gas-liquid flow reaction model. Meanwhile, economical and environmentally friendly reagents make this transformation more possible for the industrial applications.
{"title":"Visible-light catalytic aerobic oxidation of aldehydes","authors":"Jia-Le Fu , Jia-Lun Luo , Xue-Feng Zhao , Dan Zhang , Tao Wu , Hongwei Si , Peng-Fei Dai","doi":"10.1016/j.tet.2025.135039","DOIUrl":"10.1016/j.tet.2025.135039","url":null,"abstract":"<div><div>The oxidation of aldehydes to corresponding carboxylic acids catalyzed by tetra-<em>n</em>-butylammonium decatungstate (TBADT) under visible light in CH<sub>3</sub>CN or H<sub>2</sub>O have been realized for the first time. Mono-aldehydes and dialdehydes, especially aldehydes bearing with electron-withdrawing groups (e.g.: –NO<sub>2</sub>, –CO<sub>2</sub>R, –CHO, –COR, –CN, –CF<sub>3</sub>, etc.) and vulnerable groups (e.g.: –OH, -SMe, etc.) are well compatible with in moderate to good yields. And detailed mechanistic investigations have revealed the catalytic role of TBADT in the oxidation. A gram-scale synthesis has been implemented with a gas-liquid flow reaction model. Meanwhile, economical and environmentally friendly reagents make this transformation more possible for the industrial applications.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135039"},"PeriodicalIF":2.2,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415117","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 : 2025-10-30DOI: 10.1016/j.tet.2025.135033
Musarrat Fatma, Faiz Ahmed Khan
Herein, we present an intramolecular palladium catalyzed cascade electrochemical reaction in an undivided cell at room temperature to afford benzoazepine-tethered acrylate derivatives. The reaction pathway is proposed to occur initially via selective iodination followed by 7-endo-dig selective cyclization followed by Heck coupling at room temperature using palladium catalyst. The reaction features broad substrate scope with good yields under mild condition and effectively underlines the role of expanding palladium assisted electrochemical transformation.
{"title":"Electrochemically driven benzoazepine-tethered acrylate synthesis","authors":"Musarrat Fatma, Faiz Ahmed Khan","doi":"10.1016/j.tet.2025.135033","DOIUrl":"10.1016/j.tet.2025.135033","url":null,"abstract":"<div><div>Herein, we present an intramolecular palladium catalyzed cascade electrochemical reaction in an undivided cell at room temperature to afford benzoazepine-tethered acrylate derivatives. The reaction pathway is proposed to occur initially <em>via</em> selective iodination followed by 7-<em>endo-</em>dig selective cyclization followed by Heck coupling at room temperature using palladium catalyst. The reaction features broad substrate scope with good yields under mild condition and effectively underlines the role of expanding palladium assisted electrochemical transformation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135033"},"PeriodicalIF":2.2,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415048","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 : 2025-10-28DOI: 10.1016/j.tet.2025.135027
Zhen-Ye Wu , Jiang-Hong Liu , Qing Liu , Li Hai , Zhong-Zhen Yang , Yong Wu
Under visible-light irradiation, a metal-free photocatalytic system enables the generation of reactive silicon-centered radicals from a silicate reagent. The radicals undergo efficient addition to olefins, followed by polarity inversion, elimination of the leaving group, and strain-driven cyclization to afford cyclopropane-functionalized silicon products. Notably, this protocol avoids transition-metal catalysts and exhibits broad functional group tolerance. The reaction provides a sustainable strategy for constructing strained carbocycles under mild conditions.
{"title":"Photoinduced cyclopropanation of olefins via silicoborate-mediated radical transfer","authors":"Zhen-Ye Wu , Jiang-Hong Liu , Qing Liu , Li Hai , Zhong-Zhen Yang , Yong Wu","doi":"10.1016/j.tet.2025.135027","DOIUrl":"10.1016/j.tet.2025.135027","url":null,"abstract":"<div><div>Under visible-light irradiation, a metal-free photocatalytic system enables the generation of reactive silicon-centered radicals from a silicate reagent. The radicals undergo efficient addition to olefins, followed by polarity inversion, elimination of the leaving group, and strain-driven cyclization to afford cyclopropane-functionalized silicon products. Notably, this protocol avoids transition-metal catalysts and exhibits broad functional group tolerance. The reaction provides a sustainable strategy for constructing strained carbocycles under mild conditions.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135027"},"PeriodicalIF":2.2,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415049","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 : 2025-10-27DOI: 10.1016/j.tet.2025.135025
YunXia Yang, Xingang Xie, Xuegong She
In recent years, cage-like compounds have attracted extensive attention in chemistry, biology and drug discovery due to their unique spatial structures and remarkable bioactive properties. This paper systematically reviewed the structurally diverse cage-like sesquiterpenoids discovered and isolated from natural drug resources during the 2017–2025 period, focusing on their novel backbone features, extensive bioactivity profiles, and in-depth discussion of the latest advances in their total synthetic works. By analyzing the construction strategies and methodologies for these complex molecules, we aimed to provide some perspective theoretical insights and practical guidance for the total synthesis of this type of intricate natural products.
{"title":"Recent advances in total syntheses of cage-like sesquiterpenoids","authors":"YunXia Yang, Xingang Xie, Xuegong She","doi":"10.1016/j.tet.2025.135025","DOIUrl":"10.1016/j.tet.2025.135025","url":null,"abstract":"<div><div>In recent years, cage-like compounds have attracted extensive attention in chemistry, biology and drug discovery due to their unique spatial structures and remarkable bioactive properties. This paper systematically reviewed the structurally diverse cage-like sesquiterpenoids discovered and isolated from natural drug resources during the 2017–2025 period, focusing on their novel backbone features, extensive bioactivity profiles, and in-depth discussion of the latest advances in their total synthetic works. By analyzing the construction strategies and methodologies for these complex molecules, we aimed to provide some perspective theoretical insights and practical guidance for the total synthesis of this type of intricate natural products.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135025"},"PeriodicalIF":2.2,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145384503","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}
The low steric hindrance of small-substituent 2,4-diketones presents a significant challenge for effective asymmetric induction.An efficient and highly enantioselective catalytic system was developed for the Biginelli reaction to access chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones. Through catalyst screening, chiral imidodiphosphoric acid was found to outperform conventional chiral phosphoric acids. Under the optimized conditions, up to 99 % ee and 52–92 % isolated yields were achieved. This method offers a valuable strategy for the asymmetric synthesis of bioactive pyrimidine derivatives with potential pharmaceutical applicatioins.
{"title":"Asymmetric synthesis of chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones catalyzed by chiral Brønsted acid","authors":"Lingkai Kong, Zhe Li, Chunzhi Ju, Peng Wang, Guangliang Zhang, Suoqin Zhang","doi":"10.1016/j.tet.2025.134999","DOIUrl":"10.1016/j.tet.2025.134999","url":null,"abstract":"<div><div>The low steric hindrance of small-substituent 2,4-diketones presents a significant challenge for effective asymmetric induction.An efficient and highly enantioselective catalytic system was developed for the Biginelli reaction to access chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones. Through catalyst screening, chiral imidodiphosphoric acid was found to outperform conventional chiral phosphoric acids. Under the optimized conditions, up to 99 % ee and 52–92 % isolated yields were achieved. This method offers a valuable strategy for the asymmetric synthesis of bioactive pyrimidine derivatives with potential pharmaceutical applicatioins.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 134999"},"PeriodicalIF":2.2,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145384501","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}
In this work the electrooxidation of verbascoside (VB), the primary active component in Aloysia citrodora leaf extract, was investigated. The research focuse on how VB's electrooxidation, specifically its participation in a Michael addition with aryl sulfinic acids. High-performance liquid chromatography coupled with mass spectrometry (HPLC-MS) analysis has revealed the electrochemical synthesis of two sulfinic acid derivatives (mono- and bis-) using verbascoside as a core molecule. This study also proposes a plausible mechanism for the electrooxidation of verbascoside in the presence of 4-chlorosulfinic acid, which can be useful for predicting the oxidative pathway of verbascoside.
{"title":"A green electrochemical synthesis in the Aloysia citrodora leaf extract substrate","authors":"Mohadese Mohtaji , Ameneh Amani , Sadegh Khazalpour","doi":"10.1016/j.tet.2025.135021","DOIUrl":"10.1016/j.tet.2025.135021","url":null,"abstract":"<div><div>In this work the electrooxidation of verbascoside (<strong>VB</strong>), the primary active component in <em>Aloysia citrodora</em> leaf extract, was investigated. The research focuse on how VB's electrooxidation, specifically its participation in a Michael addition with aryl sulfinic acids. High-performance liquid chromatography coupled with mass spectrometry (HPLC-MS) analysis has revealed the electrochemical synthesis of two sulfinic acid derivatives (mono- and bis-) using verbascoside as a core molecule. This study also proposes a plausible mechanism for the electrooxidation of verbascoside in the presence of 4-chlorosulfinic acid, which can be useful for predicting the oxidative pathway of verbascoside.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"189 ","pages":"Article 135021"},"PeriodicalIF":2.2,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414371","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 : 2025-10-26DOI: 10.1016/j.tet.2025.135023
Hanrong Liu, Junhui Jia
Mechanochromic luminescent (MCL) materials are a class of novel intelligent materials that exhibit reversible change in luminescence color and/or intensity upon external mechanical force stimulation, demonstrating significant application potential in fields of force sensors, anti-counterfeiting materials, optical storage, bioimaging, and inkless printing, etc. Over the past few decades, in sharp contrast to the traditional fluorescence quenching phenomenon, MCL materials with enhanced luminescence effects have attracted considerable attention due to their unique “off-on” or “turn-on” behavior, where the luminescence intensity or efficiency significantly increased under mechanical force. Focusing on this intriguing property, this review summarizes the latest advances in “turn-on” MCL organic luminophores, categorizing them based on structural features and associated luminescence mechanisms. It emphasizes the critical roles of intermolecular interactions and packing modes in regulating mechanochromic behavior and mechanical force-induced luminescence enhancement performance. Furthermore, this review prospects future development directions and challenges for mechanical force-induced chromic materials with luminescence enhancement, including the development of novel high-efficiency materials, exploration of practical application potential, and in-depth investigation of underlying luminescence mechanisms.
{"title":"Mechanical force-induced luminescence enhancement and chromism of organic luminogens: synthesis, recent advances and perspectives","authors":"Hanrong Liu, Junhui Jia","doi":"10.1016/j.tet.2025.135023","DOIUrl":"10.1016/j.tet.2025.135023","url":null,"abstract":"<div><div>Mechanochromic luminescent (MCL) materials are a class of novel intelligent materials that exhibit reversible change in luminescence color and/or intensity upon external mechanical force stimulation, demonstrating significant application potential in fields of force sensors, anti-counterfeiting materials, optical storage, bioimaging, and inkless printing, <em>etc</em>. Over the past few decades, in sharp contrast to the traditional fluorescence quenching phenomenon, MCL materials with enhanced luminescence effects have attracted considerable attention due to their unique “off-on” or “turn-on” behavior, where the luminescence intensity or efficiency significantly increased under mechanical force. Focusing on this intriguing property, this review summarizes the latest advances in “turn-on” MCL organic luminophores, categorizing them based on structural features and associated luminescence mechanisms. It emphasizes the critical roles of intermolecular interactions and packing modes in regulating mechanochromic behavior and mechanical force-induced luminescence enhancement performance. Furthermore, this review prospects future development directions and challenges for mechanical force-induced chromic materials with luminescence enhancement, including the development of novel high-efficiency materials, exploration of practical application potential, and in-depth investigation of underlying luminescence mechanisms.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135023"},"PeriodicalIF":2.2,"publicationDate":"2025-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145384502","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}
A nickel-catalyzed double C–H functionalization strategy was developed for the synthesis of substituted benzothiazoles by sequential C–H functionalization of activated arenes or heteroarenes and aryl isothiocyanates. The reaction commences with triflic acid-mediated carbon–carbon bond formation, followed by nickel triflate-catalyzed intramolecular carbon–sulfur bond formation. By leveraging nickel's unique electronic and redox properties, the process achieves good selectivity and broad substrate scope with less catalyst loadings (10 mol %), while avoiding the need for expensive or toxic precious-metal catalysts.
{"title":"Nickel catalyzed cascade double C(sp2)–H/C(sp2)–H functionalization: Synthesis of benzothiazoles from aryl isothiocyanates","authors":"Bokka Srinivas, Kotari Shakeena, Durga Prasad Singuru, Karri Madhu, Gedela Rambabu, Yenigalla Phani Trivish Kumar, Santhosh Kumar Alla","doi":"10.1016/j.tet.2025.135028","DOIUrl":"10.1016/j.tet.2025.135028","url":null,"abstract":"<div><div>A nickel-catalyzed double C–H functionalization strategy was developed for the synthesis of substituted benzothiazoles by sequential C–H functionalization of activated arenes or heteroarenes and aryl isothiocyanates. The reaction commences with triflic acid-mediated carbon–carbon bond formation, followed by nickel triflate-catalyzed intramolecular carbon–sulfur bond formation. By leveraging nickel's unique electronic and redox properties, the process achieves good selectivity and broad substrate scope with less catalyst loadings (10 mol %), while avoiding the need for expensive or toxic precious-metal catalysts.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"189 ","pages":"Article 135028"},"PeriodicalIF":2.2,"publicationDate":"2025-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414369","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 : 2025-10-26DOI: 10.1016/j.tet.2025.135024
Fei Zeng , Lin-Li Tang , Fei HongYao , Qiang Shi
This review highlights the architectural innovations and multifunctional applications of amide macrocycles in supramolecular chemistry. The review delves into the architectural innovations of amide macrocycles, including cyclic peptides and aromatic amide macrocycles. Cyclic peptides, formed by the cyclization of amino acids, exhibit enhanced conformational rigidity and programmable self-assembly, enabling the formation of nanostructures like nanotubes for applications in ion transport and molecular recognition. Aromatic amide macrocycles, constructed by linking aromatic units with amide bonds, demonstrate exceptional guest selectivity and stimuli-responsive behavior, making them suitable for anion sensing, catalysis, and adaptive materials. Beyond structural design, the review explores the multifunctional frontiers of amide macrocycles, such as constructing higher-order architectures like rotaxanes, controlled self-assembly into nanostructured materials, selective ion recognition and extraction, and the development of artificial molecular channels that mimic biological transport systems. These applications showcase the potential of amide macrocycles in addressing real-world challenges. The review concludes that amide macrocycles represent a transformative platform in supramolecular chemistry, combining structural precision with dynamic functionality to open new avenues for innovation in several possible fields.
{"title":"Amide macrocycles: Architectural innovations and multifunctional frontiers in supramolecular chemistry","authors":"Fei Zeng , Lin-Li Tang , Fei HongYao , Qiang Shi","doi":"10.1016/j.tet.2025.135024","DOIUrl":"10.1016/j.tet.2025.135024","url":null,"abstract":"<div><div>This review highlights the architectural innovations and multifunctional applications of amide macrocycles in supramolecular chemistry. The review delves into the architectural innovations of amide macrocycles, including cyclic peptides and aromatic amide macrocycles. Cyclic peptides, formed by the cyclization of amino acids, exhibit enhanced conformational rigidity and programmable self-assembly, enabling the formation of nanostructures like nanotubes for applications in ion transport and molecular recognition. Aromatic amide macrocycles, constructed by linking aromatic units with amide bonds, demonstrate exceptional guest selectivity and stimuli-responsive behavior, making them suitable for anion sensing, catalysis, and adaptive materials. Beyond structural design, the review explores the multifunctional frontiers of amide macrocycles, such as constructing higher-order architectures like rotaxanes, controlled self-assembly into nanostructured materials, selective ion recognition and extraction, and the development of artificial molecular channels that mimic biological transport systems. These applications showcase the potential of amide macrocycles in addressing real-world challenges. The review concludes that amide macrocycles represent a transformative platform in supramolecular chemistry, combining structural precision with dynamic functionality to open new avenues for innovation in several possible fields.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"189 ","pages":"Article 135024"},"PeriodicalIF":2.2,"publicationDate":"2025-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414372","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}
A systematic impurity profile research concerning six observed process-related impurities of Relugolix was reported and their structures were identified on the basis of HRMS, 1H NMR, 13C NMR and HMBC NMR. In addition, a new crystal form as the strategy for minimizing these impurities to the levels accepted by ICH was described in this report.
{"title":"Identification and strategy for minimization of impurities in the synthesis of Relugolix","authors":"Xuan Wang, Ying Luo, Peng Zhang, Xueyan Zhu, Xiangkui Liu, Yinbo Chen","doi":"10.1016/j.tet.2025.134998","DOIUrl":"10.1016/j.tet.2025.134998","url":null,"abstract":"<div><div>A systematic impurity profile research concerning six observed process-related impurities of Relugolix was reported and their structures were identified on the basis of HRMS, <sup>1</sup>H NMR, <sup>13</sup>C NMR and HMBC NMR. In addition, a new crystal form as the strategy for minimizing these impurities to the levels accepted by ICH was described in this report.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"189 ","pages":"Article 134998"},"PeriodicalIF":2.2,"publicationDate":"2025-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414368","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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