The first example of an effective TfOH-catalyzed PPh3-promoted nucleophilic cyclization reaction for the synthesis of (Z)-2-imino-benzo[e ][1,3]thiazin-4-ones via benzo [c] [1,2]dithiol-3-ones and carbodiimides have been developed. The nucleophilic cyclization reaction offers new concise routes to access various functionalized (Z)-2-imino-benzothiazinones in moderate to excellent yields under mild reaction conditions, which are of biological and synthetic importance.
{"title":"TfOH-catalyzed PPh3-promoted nucleophilic cyclization reactions for the synthesis of functionalized (Z)-2-imino-benzo[e][1,3]thiazin-4-ones","authors":"Lirong Jiang, Jiayang Zhang, Xiaolu Li, Xuan Tang, Shuwen Gong, Xianqiang Huang, Guodong Shen","doi":"10.1016/j.tet.2025.134676","DOIUrl":"10.1016/j.tet.2025.134676","url":null,"abstract":"<div><div>The first example of an effective TfOH-catalyzed PPh<sub>3</sub>-promoted nucleophilic cyclization reaction for the synthesis of (<em>Z</em>)-2-imino-benzo[<em>e</em> ][1,3]thiazin-4-ones <em>via</em> benzo [<em>c</em>] [1,2]dithiol-3-ones and carbodiimides have been developed. The nucleophilic cyclization reaction offers new concise routes to access various functionalized (<em>Z</em>)-2-imino-benzothiazinones in moderate to excellent yields under mild reaction conditions, which are of biological and synthetic importance.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134676"},"PeriodicalIF":2.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858836","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 simple and efficient procedure for the synthesis of 5-acetyl-4-amino-3-(aryl)thieno[2,3-b]pyridin-6(7H)-ones by one-pot two-step reaction between 2-(1-arylethylidene)malononitriles, elemental sulfur, and Meldrum's acid in the presence of AlCl3 (15 mol %) in 1,2-dichloroethane under refluxing conditions is reported.
{"title":"Efficient one-pot four-component sequential synthesis of 5-acetyl-4-amino-3-(aryl)thieno[2,3-b]pyridin-6(7H)-ones in the presence of aluminum chloride","authors":"Hossein Mehrabi, Farzaneh Alizadeh-Bami, Zeynab Mohammadi","doi":"10.1016/j.tet.2025.134673","DOIUrl":"10.1016/j.tet.2025.134673","url":null,"abstract":"<div><div>A simple and efficient procedure for the synthesis of 5-acetyl-4-amino-3-(aryl)thieno[2,3-<em>b</em>]pyridin-6(7<em>H</em>)-ones by one-pot two-step reaction between 2-(1-arylethylidene)malononitriles, elemental sulfur, and Meldrum's acid in the presence of AlCl<sub>3</sub> (15 mol %) in 1,2-dichloroethane under refluxing conditions is reported.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134673"},"PeriodicalIF":2.1,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143856018","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 metal and additional oxidant free, visible light induced decarboxylative acylation of acenaphthenone-2-ylidene ketone has been accomplished for the first time at room temperature utilizing ambient air as the only oxidant. By using 2,4,5,6-tetra(9H-carbazol-9- yl)isophthalonitrile (4CzIPN) as a photocatalyst under mild circumstance, this acylation has been carried out without the requirement of metal reagent, conventional heating and an additional base.
{"title":"Visible-light-promoted oxidative decarboxylative acylation of acenaphthenone-2-ylidene ketones with α-keto carboxylic acids under metal, additonal oxidant and base-free condition","authors":"Tiyasa Dhar , Debasish Bera , Suvendu Maity , Chhanda Mukhopadhyay","doi":"10.1016/j.tet.2025.134674","DOIUrl":"10.1016/j.tet.2025.134674","url":null,"abstract":"<div><div>A metal and additional oxidant free, visible light induced decarboxylative acylation of acenaphthenone-2-ylidene ketone has been accomplished for the first time at room temperature utilizing ambient air as the only oxidant. By using 2,4,5,6-tetra(9H-carbazol-9- yl)isophthalonitrile (4CzIPN) as a photocatalyst under mild circumstance, this acylation has been carried out without the requirement of metal reagent, conventional heating and an additional base.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134674"},"PeriodicalIF":2.1,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143856019","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 : 2025-04-18DOI: 10.1016/j.tet.2025.134668
Zhaobo Fu, Yanting Yu, Zeguo Fang, Qian Zhang, Dong Li
A palladium-catalyzed aminocarbonylation of vinyl bromides with isocyanides was developed, which provides the α,β-unsaturated amides in moderated to good yields. Both α- and β-bromoalkenes could be applied in this method and gave the corresponding linear or branched unsaturated amides with single configuration. It provided an efficient and facile method for the synthesis of α,β-unsaturated amides from readily available feedstocks.
{"title":"Palladium-catalyzed aminocarbonylation of vinyl bromides with isocyanides for the synthesis of α,β-unsaturated amides","authors":"Zhaobo Fu, Yanting Yu, Zeguo Fang, Qian Zhang, Dong Li","doi":"10.1016/j.tet.2025.134668","DOIUrl":"10.1016/j.tet.2025.134668","url":null,"abstract":"<div><div>A palladium-catalyzed aminocarbonylation of vinyl bromides with isocyanides was developed, which provides the <em>α,β</em>-unsaturated amides in moderated to good yields. Both <em>α</em>- and <em>β</em>-bromoalkenes could be applied in this method and gave the corresponding linear or branched unsaturated amides with single configuration. It provided an efficient and facile method for the synthesis of <em>α,β</em>-unsaturated amides from readily available feedstocks.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134668"},"PeriodicalIF":2.1,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847887","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 selenylation of (benz)imidazole and related heteroarenes has been successfully achieved using PdCl2/Ag2O/Xantphos as a catalytic system. This method exploits the cooperative action of palladium and silver catalyst to activate diaryl diselenides as well as C–H bonds of (benz)imidazole and related heteroarenes, enabling the effective coupling of selenium moieties with these heteroarenes. Control experiments involving variation in catalyst loading revealed the synergistic interaction between Pd and Ag catalyst in the reaction. The unification of these robust catalytic systems ensures optimal outcome in the synthesis of a diverse array of organoselenium compounds featuring aryl-heteroaryl scaffolds.
{"title":"Direct C–H selenylation of (Benz)imidazole and related heterocycles via cooperative action of palladium and silver catalyst","authors":"Pranali Prabhakar Thakur, Manali Pawar, Mahendra Patil","doi":"10.1016/j.tet.2025.134667","DOIUrl":"10.1016/j.tet.2025.134667","url":null,"abstract":"<div><div>The selenylation of (benz)imidazole and related heteroarenes has been successfully achieved using PdCl<sub>2</sub>/Ag<sub>2</sub>O/Xantphos as a catalytic system. This method exploits the cooperative action of palladium and silver catalyst to activate diaryl diselenides as well as C–H bonds of (benz)imidazole and related heteroarenes, enabling the effective coupling of selenium moieties with these heteroarenes. Control experiments involving variation in catalyst loading revealed the synergistic interaction between Pd and Ag catalyst in the reaction. The unification of these robust catalytic systems ensures optimal outcome in the synthesis of a diverse array of organoselenium compounds featuring aryl-heteroaryl scaffolds.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134667"},"PeriodicalIF":2.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847888","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}
Amino acids and peptides have emerged as versatile organic catalysts and ligands owing to their unique structural diversity, biocompatibility, inherent chirality, and eco-friendly nature. Their applications span diverse fields, including asymmetric catalysis, metal complexation, and material science. The unique self-assembling properties of peptides are harnessed to create β-turn structures, foldamers, and nanotubes. The inherent chirality of amino acids and peptides is particularly valuable in asymmetric catalysis, enabling the development of highly stereoselective reactions crucial for pharmaceutical and fine chemical synthesis. Their ability to self-assemble into complex architectures also opens avenues for designing novel materials with tailored properties. Furthermore, the eco-friendly and biocompatible nature of these biomolecules aligns with the principles of green chemistry, making them ideal candidates for sustainable and environmentally benign processes. Synthetic amino acids and peptides hold tremendous promise as enzyme-like catalysts, capable of mimicking natural enzymatic systems to achieve remarkable catalytic efficiency and stereoselectivity. By leveraging the precise control over structure and functionality provided by synthetic modifications, researchers can create catalysts that rival or surpass traditional systems in performance. These advancements underline the potential of amino acids and peptides to revolutionize sustainable chemical processes, offering an innovative approach to addressing challenges in catalysis and material science. This review summarizes the advances in this domain, focusing on research published between 2018 and 2025 including selected amino acid examples from a broader body of research.
{"title":"Organic catalysts and ligands derived from amino acids and peptides","authors":"Lipat Kaur , Karuna Thakare , Aman Singh Barahdia , Salil Pophali , Rajkumar Misra, Rahul Jain","doi":"10.1016/j.tet.2025.134671","DOIUrl":"10.1016/j.tet.2025.134671","url":null,"abstract":"<div><div>Amino acids and peptides have emerged as versatile organic catalysts and ligands owing to their unique structural diversity, biocompatibility, inherent chirality, and eco-friendly nature. Their applications span diverse fields, including asymmetric catalysis, metal complexation, and material science. The unique self-assembling properties of peptides are harnessed to create β-turn structures, foldamers, and nanotubes. The inherent chirality of amino acids and peptides is particularly valuable in asymmetric catalysis, enabling the development of highly stereoselective reactions crucial for pharmaceutical and fine chemical synthesis. Their ability to self-assemble into complex architectures also opens avenues for designing novel materials with tailored properties. Furthermore, the eco-friendly and biocompatible nature of these biomolecules aligns with the principles of green chemistry, making them ideal candidates for sustainable and environmentally benign processes. Synthetic amino acids and peptides hold tremendous promise as enzyme-like catalysts, capable of mimicking natural enzymatic systems to achieve remarkable catalytic efficiency and stereoselectivity. By leveraging the precise control over structure and functionality provided by synthetic modifications, researchers can create catalysts that rival or surpass traditional systems in performance. These advancements underline the potential of amino acids and peptides to revolutionize sustainable chemical processes, offering an innovative approach to addressing challenges in catalysis and material science. This review summarizes the advances in this domain, focusing on research published between 2018 and 2025 including selected amino acid examples from a broader body of research.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134671"},"PeriodicalIF":2.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847889","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 : 2025-04-16DOI: 10.1016/j.tet.2025.134672
Yaoyao Liu , Yating Zhang , Fan Zhang, Mengqi Wang, Jun Xu
In continuation of our research interest in oxidation of indoles, we further explore the direct oxidation of indoles to 3-halooxindoles promoted by the combination of NCS, H2O, and NaIO4, thereby suppressing the competitive semipinacol rearrangement reaction. This methodology was demonstrated to be a robust protocol mainly consisting of broad substrate scope and excellent functional compatibility, thus enabling the preparation of high added-value versatile building blocks susceptible to further functionalization. Additionally, synthesis of natural product CPC-1 from commercially available starting materials has also been achieved in four steps using this reaction as a key transformation.
{"title":"Assembly of 3-halooxindoles via interrupted semipinacol Rearrangement: Enabling concise total synthesis of CPC-1","authors":"Yaoyao Liu , Yating Zhang , Fan Zhang, Mengqi Wang, Jun Xu","doi":"10.1016/j.tet.2025.134672","DOIUrl":"10.1016/j.tet.2025.134672","url":null,"abstract":"<div><div>In continuation of our research interest in oxidation of indoles, we further explore the direct oxidation of indoles to 3-halooxindoles promoted by the combination of NCS, H<sub>2</sub>O, and NaIO<sub>4</sub>, thereby suppressing the competitive semipinacol rearrangement reaction. This methodology was demonstrated to be a robust protocol mainly consisting of broad substrate scope and excellent functional compatibility, thus enabling the preparation of high added-value versatile building blocks susceptible to further functionalization. Additionally, synthesis of natural product CPC-1 from commercially available starting materials has also been achieved in four steps using this reaction as a key transformation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134672"},"PeriodicalIF":2.1,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847884","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}
Natural triterpenoids represent a prominent class of secondary metabolites widely distributed in terrestrial plants and marine organisms. Characterized by intricate polycyclic architectures, these compounds exhibit a diverse array of significant biological activities that have garnered sustained research interest in both organic synthesis and medicinal chemistry communities. The strategic implementation of skeletal construction and late-stage functionalization methodologies have emerged as cornerstones in natural product synthesis. These approaches are frequently coupled with high-efficiency chemical transformations, including but not limited to electrocyclic processes, cycloaddition reactions, polyene cyclization cascades, skeletal rearrangements, and late-stage C(sp3)-H oxidations. Such innovative strategies have not only facilitated the total syntheses of complex triterpenoid but also significantly advanced the development of triterpenoid chemistry. This comprehensive review systematically examines the methodological breakthroughs and synthetic applications of skeletal construction tactics and late-stage functionalization in triterpenoid synthesis over the past decade.
{"title":"Recent advances in skeletal construction strategies and late-stage functionalization in the synthesis of natural triterpenoids","authors":"Jiang-Li Huang, Kun Li, Tong-Ling Cha, Dashan Li, Wen-Jing Wang, Li-Dong Shao","doi":"10.1016/j.tet.2025.134666","DOIUrl":"10.1016/j.tet.2025.134666","url":null,"abstract":"<div><div>Natural triterpenoids represent a prominent class of secondary metabolites widely distributed in terrestrial plants and marine organisms. Characterized by intricate polycyclic architectures, these compounds exhibit a diverse array of significant biological activities that have garnered sustained research interest in both organic synthesis and medicinal chemistry communities. The strategic implementation of skeletal construction and late-stage functionalization methodologies have emerged as cornerstones in natural product synthesis. These approaches are frequently coupled with high-efficiency chemical transformations, including but not limited to electrocyclic processes, cycloaddition reactions, polyene cyclization cascades, skeletal rearrangements, and late-stage C(sp<sup>3</sup>)-H oxidations. Such innovative strategies have not only facilitated the total syntheses of complex triterpenoid but also significantly advanced the development of triterpenoid chemistry. This comprehensive review systematically examines the methodological breakthroughs and synthetic applications of skeletal construction tactics and late-stage functionalization in triterpenoid synthesis over the past decade.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134666"},"PeriodicalIF":2.1,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143843387","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}
Fluorophores capable of exhibiting aggregation induced emission enhancement (AIEE) belong to an extremely important class of molecular materials. With the widespread application that ranges from medicinal usage to light emitting device fabrications, AIEE systems are known to offer a plethora of properties which has made them as one of the most heavily explored materials in the recent past. In the present work, we have prepared three naphthalimide derivatives that form self-assembled structures in DMSO/H2O mixtures and exhibit strong AIEE behavior. Steady-state and time-resolved fluorescence spectroscopic studies have been performed to explore the self-assembly process and its impact on the fluorescence and excited state lifetime.
{"title":"Supramolecular assembly-based tuning of optical properties of pyrrolidine, pyrimidine and morpholine functionalized naphthalimides","authors":"Viral Khatri , Alisha Sengupta , Raj Dave , Rajesh Bhosale , Nidhi Gour , Deepak Asthana","doi":"10.1016/j.tet.2025.134655","DOIUrl":"10.1016/j.tet.2025.134655","url":null,"abstract":"<div><div>Fluorophores capable of exhibiting aggregation induced emission enhancement (AIEE) belong to an extremely important class of molecular materials. With the widespread application that ranges from medicinal usage to light emitting device fabrications, AIEE systems are known to offer a plethora of properties which has made them as one of the most heavily explored materials in the recent past. In the present work, we have prepared three naphthalimide derivatives that form self-assembled structures in DMSO/H<sub>2</sub>O mixtures and exhibit strong AIEE behavior. Steady-state and time-resolved fluorescence spectroscopic studies have been performed to explore the self-assembly process and its impact on the fluorescence and excited state lifetime.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134655"},"PeriodicalIF":2.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143843388","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 : 2025-04-12DOI: 10.1016/j.tet.2025.134657
Gangarajulu Kesavulu, Kavirayani R. Prasad
A short synthetic sequence for the synthesis of D-lyxo and D-xylo-phytosphingosine and fully acylated sphingofungin B methyl ester is presented. The key reaction in the synthesis is the addition of lithio tris(methylthio)methane to sulfinimine to install the required chiral amino acid/amino alcohol component.
{"title":"Total synthesis of D-lyxo- and D-xylo-phytospingosines and fully acylated sphingofungin B","authors":"Gangarajulu Kesavulu, Kavirayani R. Prasad","doi":"10.1016/j.tet.2025.134657","DOIUrl":"10.1016/j.tet.2025.134657","url":null,"abstract":"<div><div>A short synthetic sequence for the synthesis of D-<em>lyxo</em> and D-<em>xylo</em>-phytosphingosine and fully acylated sphingofungin B methyl ester is presented. The key reaction in the synthesis is the addition of lithio tris(methylthio)methane to sulfinimine to install the required chiral amino acid/amino alcohol component.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"180 ","pages":"Article 134657"},"PeriodicalIF":2.1,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834636","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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