{"title":"Regio- and Stereoselective [3 + 2] cycloaddition of Isatogens with functionalized alkenes and its application to the synthesis of Halichrome A","authors":"Nanaka Ishihara , Ryu Fukuoka , Shinji Harada , Kenzo Yamatsugu , Shigeru Arai","doi":"10.1016/j.tetlet.2025.155626","DOIUrl":"10.1016/j.tetlet.2025.155626","url":null,"abstract":"<div><div>We investigated regio- and stereoselective [3 + 2] cycloaddition reactions of isatogens and found that various heteroatom-substituted C<img>C double bonds are applicable to provide the corresponding heterocycles with regio- and stereoselective manner. Synthetic application of the products towards various heterocycles and the total synthesis of halichrome A is accomplished.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"167 ","pages":"Article 155626"},"PeriodicalIF":1.5,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144242318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiting Li , Feng Hao , Wenxuan Wu , Xiaoyan Zhou , Liyun Jiang , Huawen Wang , Kaida Li , Liang Deng , Le Cai
{"title":"Design, synthesis and Aphicidal activity of novel Pentafluorophenyl erivatives against Brevicoryne brassicae","authors":"Jiting Li , Feng Hao , Wenxuan Wu , Xiaoyan Zhou , Liyun Jiang , Huawen Wang , Kaida Li , Liang Deng , Le Cai","doi":"10.1016/j.tetlet.2025.155605","DOIUrl":"10.1016/j.tetlet.2025.155605","url":null,"abstract":"<div><div>As the global population increases, food security becomes an urgent concern, with pest infestations posing a major threat to agricultural productivity. <em>Brevicoryne brassicae</em>, a harmful pest to cruciferous crops, not only damages plants directly but also acts as a vector for plant viruses. Over-reliance on pesticides has led to the development of pest resistance, prompting the need for novel insecticides. This study explores the incorporation of the pentafluorobenzene fragment, known for its electron-withdrawing properties and stability, into agricultural chemical molecules to enhance their insecticidal efficacy and combat resistance. A new class of compounds, combining pentafluorobenzene with pyrrole, was synthesized and evaluated for aphicidal activity against cabbage aphids. The results show that <strong>SO</strong>-type compounds exhibit potent insecticidal activity, with compound <strong>SO-3</strong> outperforming imidacloprid in terms of aphid mortality and binding affinity to AChBP. Molecular docking analysis revealed that <strong>SO-3</strong> forms six hydrogen bonds with AChBP, which may contribute to its superior efficacy. Additionally, pharmacokinetic modeling of <strong>SO-3</strong> predicted favorable lipophilicity and promising oral bioavailability. These findings suggest that the pentafluorobenzene-containing compounds could provide a promising avenue for the development of more effective agrochemicals to address pest resistance and improve crop protection strategies.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"164 ","pages":"Article 155605"},"PeriodicalIF":1.5,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143942037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis of Oxazoline-spirocyclohexadienone via Electrochemical Dearomatization of Phenol Derivatives","authors":"Long-Hao Zhu , Yuan-Zheng Cheng , Shu-Li You","doi":"10.1016/j.tetlet.2025.155622","DOIUrl":"10.1016/j.tetlet.2025.155622","url":null,"abstract":"<div><div>Oxazoline and spirocyclohexadienone moieties are prevalent in natural products and biologically active molecules. Herein, we report an efficient method for the synthesis of oxazoline-spirocyclohexadienones via electrochemistry-mediated oxidative dearomatization of phenol derivatives, utilizing amide side chains as nucleophiles. This approach features the employment of anodic oxidation strategy, circumventing the need for traditional oxidizing agents. A diverse range of oxazoline-spirocyclohexadienones are obtained in moderate to excellent yields (15–97 %). Cyclic voltammetry experiments reveal that the solvent plays a crucial role in this transformation and this reaction involves two consecutive single-electron transfer events.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"164 ","pages":"Article 155622"},"PeriodicalIF":1.5,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143942039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jie Zeng , Houwen Zhou , Shenghao Wang , Fenghua Zhang , Fei Li , Jingjing Wang , Lin Li , Tianbao Dong , Mingyue Cui , Feng Li
{"title":"Silver-catalyzed direct decarboxylative CH functionalization of azauracils with aliphatic carboxylic acids","authors":"Jie Zeng , Houwen Zhou , Shenghao Wang , Fenghua Zhang , Fei Li , Jingjing Wang , Lin Li , Tianbao Dong , Mingyue Cui , Feng Li","doi":"10.1016/j.tetlet.2025.155619","DOIUrl":"10.1016/j.tetlet.2025.155619","url":null,"abstract":"<div><div>We propose a novel method for the C<img>H alkylation of azauracils using aliphatic carboxylic acids as alkyl radical precursors, catalyzed by silver. This technique marks a substantial progress in organic synthesis, providing a flexible and effective route for azauracils modification. The method has been successfully applied to a diverse array of primary, secondary and tertiary carboxylic acids, highlighting its broad utility and reliability. The applicability of this method allows the preparation of a range of alkylated azauracil derivatives, which are potential intermediates for the creation of new pharmaceuticals, agrochemicals, and materials.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"163 ","pages":"Article 155619"},"PeriodicalIF":1.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Swarnali Ghosh , Anindita Sarkar , Rahul Dev Mandal , Asish R. Das
{"title":"Innovative advancements in transition metal-catalyzed C(sp2)-H bond activation of phthalazinone: Unlocking the gateway to diverse hybrid polyheterocyclic architectures","authors":"Swarnali Ghosh , Anindita Sarkar , Rahul Dev Mandal , Asish R. Das","doi":"10.1016/j.tetlet.2025.155618","DOIUrl":"10.1016/j.tetlet.2025.155618","url":null,"abstract":"<div><div>Phthalazinones, a fused diaza heterocycles have been recognized as remarkable structural leads in medicinal chemistry owing to its wider application in pharmaceutical and agrochemical industries. Moreover, having unique structural feature and potent biological activities, this scaffold allures the attention of synthetic chemists toward selective activation and functionalization of C<img>H bonds to synthesize its fused polycyclic frameworks. To attain this goal, transition-metal-catalyzed directing group-assisted inert Csp<sup>2</sup>-H functionalization has pooled up powerful strategies into modern chemistry toolbox in the last decade. The regioselective activation and annulation of C<img>H bonds are improving the synthetic approach and revolutionizing conventional cross-coupling techniques in current research. In this domain, the selective functionalization of C<img>H bonds in heteroarenes is primarily accomplished by Ru, Rh, Ir, and Pd metal complexes and their salts. This review primarily focuses on recent developments in the selective activation and functionalization of C<img>H bonds and the annulation of phthalazinones to synthesize their fused polycyclic frameworks. It explores their interactions with metal catalysts, along with various coupling partners such as amides, imides, ynones, vinylene carbonates, propargyl alcohols, alkenes, and alkynes which in turn led to the formation of different types of C<img>C and C<img>N bonds through selective C<img>H bond activation and subsequent annulation leading to pi-extended heterocycles.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"163 ","pages":"Article 155618"},"PeriodicalIF":1.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143917579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kemparajegowda , Rajaghatta N. Suresh , Toreshettahally R. Swaroop , Muddegowda Umashankara , Kempegowda Mantelingu , Kanchugarakoppal S. Rangappa
{"title":"Electrochemical synthesis of 2,5-disubstituted-1,3,4-thiadiazoles via oxidative cyclization of benzothiohydrazides and aldehydes catalyzed by tetra-n-butylammonium iodide","authors":"Kemparajegowda , Rajaghatta N. Suresh , Toreshettahally R. Swaroop , Muddegowda Umashankara , Kempegowda Mantelingu , Kanchugarakoppal S. Rangappa","doi":"10.1016/j.tetlet.2025.155606","DOIUrl":"10.1016/j.tetlet.2025.155606","url":null,"abstract":"<div><div>In this letter, we present the synthesis of 2,5-disubstituted-1,3,4-thiadiazoles by the oxidative cyclization reaction between benzothiohydrazides and aldehydes. The reaction mixture is electrolyzed by using reticulated vitreous carbon (RVC) and platinum as anode and cathode respectively. The tetra-<em>n</em>-butylammonium iodide played dual role as supporting electrolyte as well as catalyst. Further, this method is an example for green organic synthesis since it avoids the need of stoichiometric amount of oxidants and atom economies are high.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"163 ","pages":"Article 155606"},"PeriodicalIF":1.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Tamaru reaction-based approach towards the synthesis of muscone and analogues using renewable sources","authors":"Santosh J. Gharpure, Saidurga Prasad Kommyreddy","doi":"10.1016/j.tetlet.2025.155593","DOIUrl":"10.1016/j.tetlet.2025.155593","url":null,"abstract":"<div><div>Muscone is considered as the king of fragrances, due to its rare occurrence and exotic nature, many attempts have been made to synthesise musk analogues. The presence of methyl group at the C-3 position from ketone imparts the musk character to the molecule. The Tamaru reaction (Ni-catalysed reductive coupling of aldehyde and 1,3-dienes) is used as the key step for the installation of the methyl group in an efficient manner to afford the RCM precursor diene. A short three step sequence involving oxidation, RCM and reduction gave a highly efficient access to muscone and analogues. Both the precursors, namely, the aldehyde and isoprene are derived from renewable resource.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"163 ","pages":"Article 155593"},"PeriodicalIF":1.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Edward T. Ledingham, Johannes Puschnig, Ben W. Greatrex
{"title":"Stereoselective access to bioactive cyclopropanes (+)-PPCC and (1R,2S)-2-aminomethyl-1-arylcyclopropane-1-carboxamides from (−)-levoglucosenone","authors":"Edward T. Ledingham, Johannes Puschnig, Ben W. Greatrex","doi":"10.1016/j.tetlet.2025.155620","DOIUrl":"10.1016/j.tetlet.2025.155620","url":null,"abstract":"<div><div>The chiral synthon (−)-levoglucosenone (LGO) obtained from cellulose pyrolysis has been transformed into two known bioactive compounds: the serotonin-norepinephrine-dopamine reuptake inhibitor (1<em>R</em>,2<em>S</em>)-2-(aminomethyl)-<em>N</em>,<em>N</em>-diethyl-1-(naphthalen-2-yl)cyclopropane-1-carboxamide and the σ<sub>−</sub>receptor ligand (+)-PPCC. The key steps in the process were the arylation of an LGO derivative via a Suzuki-Miyaura cross-coupling reaction, then cyclopropanation under Johnson-Corey-Chaykovsky conditions. Dehomologation was achieved using Baeyer-Villiger and NaIO<sub>4</sub> mediated oxidation, and then functional group interconversion gave the bioactive cyclopropanes. Several derivatives of each target were developed demonstrating the versatility of the process for aryl and amine group substitution.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"163 ","pages":"Article 155620"},"PeriodicalIF":1.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143873717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiyan Ren , Mengyao Xue , Xintong Yang , Yuting Yan , Kun Zhang , Jianhui Huang
{"title":"Synthesis of chiral Azetidine and its application in asymmetric synthesis","authors":"Xiyan Ren , Mengyao Xue , Xintong Yang , Yuting Yan , Kun Zhang , Jianhui Huang","doi":"10.1016/j.tetlet.2025.155617","DOIUrl":"10.1016/j.tetlet.2025.155617","url":null,"abstract":"<div><div>Azetidine is a four-membered nitrogen-containing heterocycle, which has been utilized broadly in synthetic and medicinal chemistry. The use of azetidines in asymmetric catalysis remains largely unexplored, making this approach both innovative and promising for advancing the field. In this study, we designed and synthesized chiral bidentate azetidine pyridine hybrid ligands. A Pd-catalyzed asymmetric arylation of sulfonylimine with phenylboronic acid was examined using these new ligands. The chiral sulfonamides were obtained in excellent yields with low to good enantioselectivity (60:40 to 95:5 er).</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"163 ","pages":"Article 155617"},"PeriodicalIF":1.5,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143860185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}