TetrahedronPub Date : 2025-09-06DOI: 10.1016/j.tet.2025.134917
Edson de Oliveira Lima Filho , Raquel Nery Simão , Marcela Cristina Pereira de Barros , Guilherme Pereira Guedes , Vitor Francisco Ferreira , Fernando de Carvalho da Silva
{"title":"Stoichiometry-controlled chemoselective mechanochemical indolation of 1,2-naphthoquinones under metal- and solvent-free conditions","authors":"Edson de Oliveira Lima Filho , Raquel Nery Simão , Marcela Cristina Pereira de Barros , Guilherme Pereira Guedes , Vitor Francisco Ferreira , Fernando de Carvalho da Silva","doi":"10.1016/j.tet.2025.134917","DOIUrl":"10.1016/j.tet.2025.134917","url":null,"abstract":"<div><div>In this study, we report the development of a novel methodology for the synthesis of stoichiometry-controlled chemoselective of fifteen (mono or tris)-indole-naphthalen(di)one derivatives by mechanochemical indolation of 1,2-naphthoquinone. The reactions were conducted under solvent-free conditions using the mechanochemical technique. Notably, the method enables selective control over the formation of both symmetric and non-symmetric trisubstituted products.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134917"},"PeriodicalIF":2.2,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007636","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}
TetrahedronPub Date : 2025-09-06DOI: 10.1016/j.tet.2025.134933
Jialu Liu , Fanyuan Meng , Danfeng He , Keyue Xu , Wenjing Xiong , Weiguo Zhu
{"title":"Synthesis and characterization of electroluminescent materials: Dinuclear platinum complexes featuring 2-naphthylisoquinoline cyclometalating ligands","authors":"Jialu Liu , Fanyuan Meng , Danfeng He , Keyue Xu , Wenjing Xiong , Weiguo Zhu","doi":"10.1016/j.tet.2025.134933","DOIUrl":"10.1016/j.tet.2025.134933","url":null,"abstract":"<div><div>(2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-PhOXT)<sub>2</sub>, (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-<sup>t</sup>BuOXT)<sub>2</sub> (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-C<sub>6</sub>OXT)<sub>2</sub> and (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-C<sub>12</sub>OXT)<sub>2</sub>, were designed and synthesized, featuring 2-naphthylisoquinoline as the chelating ligand and arylthioxadiazole as the auxiliary ligand. The results showed that the photoluminescence quantum yield (PLQY) of these four dinuclear platinum complexes in dichloromethane solution were 8.2 %, 13.7 %, 18.3 % and 12.6 %, respectively. In pure thin films, their luminescence lifetimes were 1435, 554, 448, and 1266 ns, respectively. Meanwhile, the (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-PhOXT)<sub>2</sub>-, (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-<sup>t</sup>BuOXT)<sub>2</sub>-, (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-C<sub>6</sub>OXT)<sub>2</sub>- and (2niq)<sub>2</sub>Pt<sub>2</sub>(<em>μ</em>-C<sub>12</sub>OXT)<sub>2</sub>-doped polymer light-emitting devices (PLEDs) exhibited deep-red to near-infrared electroluminescence characteristics with emission peaks in the range of 686–706 nm. The maximum external quantum efficiencies (<em>EQE</em>s) were 3.00 %, 3.89 %, 5.03 %, and 5.16 %, respectively. The results revealed that device performance improved with increasing alkyl chain length of the auxiliary ligand, which might be attributed to enhanced charge transport properties. This work provided new insights into the design of efficient deep-red to near-infrared luminescent platinum complexes by introducing alkyl chains into the auxiliary ligands. It offered a novel strategy for modulating the <em>EQE</em>s of the devices based on these platinum complexes from the perspective of auxiliary ligands, thereby advancing PLED applications.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134933"},"PeriodicalIF":2.2,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145045658","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}
{"title":"A review on structural modifications of parthenin extracted from Parthenium hysterophorus L","authors":"Navneet Kaur , Loveleen Kaur , Manvinder Kaur , Harvinder Singh Sohal , Ajay Sharma , Gopal Singh Attar , Haesook Han , Pradip K. Bhowmik","doi":"10.1016/j.tet.2025.134919","DOIUrl":"10.1016/j.tet.2025.134919","url":null,"abstract":"<div><div>Parthenin is a sesquiterpene lactone extracted from <em>Parthenium hysterophorus</em> that possesses a broad spectrum of biological activities, including anti-inflammatory, antimicrobial, anticancer, and allelopathic properties. However, its clinical applications are hindered by cytotoxicity, poor solubility, low bioavailability, and instability in physiological conditions. To address these challenges, numerous structural modifications have been explored to improve its pharmacokinetic properties while enhancing its therapeutic potential. This review provides a comprehensive overview of the chemical modifications of parthenin, including hydroxylation, halogenation, Michael addition, and lactone ring alterations. Modifications, particularly in the lactone and cyclopentenone rings, can significantly enhance its anticancer, antimicrobial, and anti-inflammatory activities while reducing toxicity. The review also highlights recent pharmacological advancements and outlines promising directions for future drug development based on the parthenin derivatives. Overall, the study underscores the value of parthenin and its derivatives as innovative therapeutic agents and contributes to the progress of natural product-based drug design.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134919"},"PeriodicalIF":2.2,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020124","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}
TetrahedronPub Date : 2025-09-04DOI: 10.1016/j.tet.2025.134918
Khalid Boujdi , Yassine El Baraka , Ghanem Hamdoun , Nabil El Brahmi , Saïd El Kazzouli
{"title":"Functionalization of indazoles and azaindazoles via palladium-catalyzed cross-coupling and transition metal-free C–H activation: current advances and applications – an eight-year update","authors":"Khalid Boujdi , Yassine El Baraka , Ghanem Hamdoun , Nabil El Brahmi , Saïd El Kazzouli","doi":"10.1016/j.tet.2025.134918","DOIUrl":"10.1016/j.tet.2025.134918","url":null,"abstract":"<div><div>The functionalization of indazoles and azaindazoles is an important area of research in medicinal chemistry and materials science. This review provides an overview of recent advancements in indazole and azaindazole framework modification, emphasizing halogenation, functionalization using palladium-catalyzed strategies as well as emerging transition metal-free approaches. It explores various methodologies for synthesizing biologically active compounds and functional materials, highlighting the importance of regioselectivity in these processes. This review also offers insights into the current state of the field and identifies promising directions for future research. The aim is to provide more sustainable and efficient synthetic pathways for indazole and azaindazole derivatives.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134918"},"PeriodicalIF":2.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004760","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}
TetrahedronPub Date : 2025-09-04DOI: 10.1016/j.tet.2025.134929
Chao Yao , Xueyan Chen , Chuang Qu , Yan Zhao , Yue-Ming Li
{"title":"A new type of chiral ligands: Design and the evaluation of their performance in catalytic asymmetric reactions","authors":"Chao Yao , Xueyan Chen , Chuang Qu , Yan Zhao , Yue-Ming Li","doi":"10.1016/j.tet.2025.134929","DOIUrl":"10.1016/j.tet.2025.134929","url":null,"abstract":"<div><div>A new type of proline-based chiral ligands were designed and prepared starting from 8-hydroxy-2-methylquinoline and derivatization of <span>l</span>-proline. Coupling of these two parts yielded the desired chiral ligands in good isolated yields. The performance of these chiral ligands was evaluated using enantioselective addition of diethylzinc to aromatic aldehydes as model reactions. Under the optimized conditions, enantioselective addition of diethylzinc to aromatic aldehydes proceeded readily, giving the desired chiral alcohols in high yields and up to 97 % ee's.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134929"},"PeriodicalIF":2.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061101","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}
TetrahedronPub Date : 2025-09-03DOI: 10.1016/j.tet.2025.134913
Jian Wang , Xiaoyue Chen , Xiaole Ni , Zhen Zhang , Jinhong He , Liming Shao
{"title":"FeCl3/I2-catalyzed tandem aerobic oxidative annulation of α-aminoketone hydrochlorides with aldehydes: synthesis of substituted oxazoles","authors":"Jian Wang , Xiaoyue Chen , Xiaole Ni , Zhen Zhang , Jinhong He , Liming Shao","doi":"10.1016/j.tet.2025.134913","DOIUrl":"10.1016/j.tet.2025.134913","url":null,"abstract":"<div><div>A facile and efficient method for the synthesis of oxazoles has been developed through FeCl<sub>3</sub>/I<sub>2</sub>-catalyzed tandem aerobic oxidative annulation of α-aminoketone hydrochlorides with aldehydes. The reaction employs commercially available α-aminoketone hydrochlorides and aldehydes as the starting materials, offering notable advantages including operational simplicity, one-pot synthesis, low cost, broad scope, and good functional group tolerance. The synthetic utility has been demonstrated by the syntheses of 33 examples of oxazoles in yields up to 92 %. Furthermore, the protocol was successfully applied to gram-scale synthesis and to the one-step synthesis of the natural product oxytrofalcatin C.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134913"},"PeriodicalIF":2.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020121","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}
{"title":"Unsupported nanoporous platinum catalyst for the chemoselective hydrogenation of imines and reductive amination of benzaldehydes and anilines","authors":"Wenfei Tong , Ruyi Jiang , Wanguo Wei , Tienan Jin , Xiaojun Zheng , Yuhui Zhao , Zhiqiang Zhang","doi":"10.1016/j.tet.2025.134912","DOIUrl":"10.1016/j.tet.2025.134912","url":null,"abstract":"<div><div>The development of efficient heterogeneous catalysts for selective hydrogenation imines and reductive amination remains highly desirable in synthetic chemistry. Herein, we report a high-performance unsupported nanoporous platinum (PtNPore) catalyst for the chemoselective hydrogenation of imines and reductive amination of benzaldehydes with anilines, affording the corresponding secondary amines in good to excellent yields. Notably, the PtNPore catalyst exhibits remarkable chemoselectivity, preserving sensitive functional groups such as Cl and Br under the reaction conditions. Furthermore, the system demonstrates broad applicability, successfully enabling the N-alkylation of nitrobenzene with aldehydes to deliver secondary amines in high yield. The unsupported PtNPore can be reusable at least four times without obvious loss of catalytic activity. This work highlights the potential of unsupported nanoporous metals as robust and selective catalysts for sustainable amine synthesis.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134912"},"PeriodicalIF":2.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997377","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}
TetrahedronPub Date : 2025-09-03DOI: 10.1016/j.tet.2025.134915
Chao-Tun Cao, Xueqian Peng, Zhao Zeng, Chenzhong Cao
{"title":"Direct synthesis of 2-(benzylamino)benzoic acids by using benzaldehydes and 2-aminobenzoic acids with catalysis of p-toluenesulfonic acid","authors":"Chao-Tun Cao, Xueqian Peng, Zhao Zeng, Chenzhong Cao","doi":"10.1016/j.tet.2025.134915","DOIUrl":"10.1016/j.tet.2025.134915","url":null,"abstract":"<div><div>Direct reductive amination of carbonyl compounds is a promising method for the synthesis of amine derivatives. Usually, stoichiometric reducing agents generate significant waste products, some of which are hazardous and difficult to handle. Therefore, it is highly desirable to synthesize amines using reducing agents that cause low environmental pollution and minimize hazardous by-products. In this work, It was discovered that substituted benzaldehydes and substituted 2-aminobenzoic acids can be directly converted into substituted 2-(benzylamino)benzoic acids using <em>p</em>-toluenesulfonic acid (TsOH) as a catalyst in a one-pot method, where the only by-product is substituted benzoic acid. The reaction mechanism was investigated, and the results showed that the Schiff base's carbon-nitrogen double bond is reduced by benzaldehyde under TsOH catalysis, resulting in 2-(benzylamino)benzoic acid. This phenomenon was not observed previously. The advantage of this method lies in its mild reaction conditions, as it requires neither metal catalysis nor additional reducing agents.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134915"},"PeriodicalIF":2.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004759","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}
TetrahedronPub Date : 2025-09-02DOI: 10.1016/j.tet.2025.134906
Lei Zhao , Yi-Lei Huang , Peng Xie , Huang-Di Feng , Guan Wang , Jun-Hai Huang
{"title":"Facile synthesis of diverse 2-aminopyrimidines by phosphorus oxychloride-promoted C2-selective amination of pyrimidines","authors":"Lei Zhao , Yi-Lei Huang , Peng Xie , Huang-Di Feng , Guan Wang , Jun-Hai Huang","doi":"10.1016/j.tet.2025.134906","DOIUrl":"10.1016/j.tet.2025.134906","url":null,"abstract":"<div><div>2-Aminopyrimidines play a significant role in the composition of small-molecule drugs. The direct synthesis of 2-aminopyrimidines from pyrimidine has posed a challenge due to the complexities associated with achieving C2-selective amination of pyrimidines. This study presents the successful C2-selective amination reaction of pyrimidine utilizing phosphorus oxychloride as a regioselective controller. The resulting 2-chloropyrimidine intermediate can be further transformed into a variety of 2-aminopyrimidine derivatives in an aqueous environment.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134906"},"PeriodicalIF":2.2,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004761","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}
TetrahedronPub Date : 2025-09-02DOI: 10.1016/j.tet.2025.134910
Tianwei Liu , Haiying Wang
{"title":"Synthesis of tetrahydroquinoline via hydrosilylation-transfer hydrogenation of quinoline with silane and water catalyzed by a switchable Lewis and Brønsted acid system","authors":"Tianwei Liu , Haiying Wang","doi":"10.1016/j.tet.2025.134910","DOIUrl":"10.1016/j.tet.2025.134910","url":null,"abstract":"<div><div>Employing a single catalyst in various forms within a reaction system to synergistically catalyzed reactions represent an efficient and convenient synthetic strategy. Using B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> as a catalyst, the direct synthesis of tetrahydroquinoline was achieved through the catalyzed hydrosilylation and transfer hydrogenation of quinoline with silane in the presence of water. Through control experiments, it has been demonstrated that this reaction was catalyzed synergistically by both the Lewis acid and Brønsted acid. The Lewis acid B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> catalyzes the hydrosilylation of quinoline, yielding a <em>N</em>-silylated-dihydroquinoline. Meanwhile, the Brønsted acid B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>·H<sub>2</sub>O mediates the transfer hydrogenation of <em>N</em>-silylated-dihydroquinoline in the presence of quinoline and silane, forming the <em>N</em>-silylated-tetrahydroquinoline, ultimately yielding the desired product upon subsequent hydrolysis. Compared to traditional methods of reducing quinoline to tetrahydroquinoline using H<sub>2</sub>, this reaction features mild conditions and high efficiency. Compared with other reaction systems for quinoline reduction using B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> as the catalyst, silanes and/or boranes as hydride sources, and amines and/or indoles as proton sources, this method employs water as the proton source, exhibiting the advantages of being green and cost-effective. Moreover, this system demonstrates that in the presence of water, B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> can switch between Lewis acid and Brønsted acid forms and exhibit a new mode of catalytic reaction.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134910"},"PeriodicalIF":2.2,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997379","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}