TetrahedronPub Date : 2025-07-10DOI: 10.1016/j.tet.2025.134810
Harbi Tomah Al-Masri , Ziad Moussa , Akram Ali Almejled
{"title":"Novel Hg(II) metal complexes of chelating phosphinopyridylamine and its selenide ligands: Synthesis, characterization, and X-ray structures","authors":"Harbi Tomah Al-Masri , Ziad Moussa , Akram Ali Almejled","doi":"10.1016/j.tet.2025.134810","DOIUrl":"10.1016/j.tet.2025.134810","url":null,"abstract":"<div><div>The reaction of 4-Me–C<sub>5</sub>H<sub>3</sub>N–2-NH(PPh<sub>2</sub>) (<strong>1</strong>) and monooxidized selenoyl (4-CH<sub>3</sub>)C<sub>6</sub>H<sub>3</sub>N-2-NH(P(Se)Ph<sub>2</sub>) (<strong>2</strong>) ligands with HgX<sub>2</sub> (X = Cl, I) in acetone yielded the dimeric complexes [HgCl<sub>2</sub>]<sub>2</sub>[{<strong>1</strong>-κ<sup>2</sup><em>P,N</em>}{<strong>1</strong>-κ<em>P</em>}] (<strong>3</strong>) and [HgI<sub>2</sub>{<strong>1</strong>-κ<sup>2</sup><em>P,N</em>}]<sub>2</sub> (<strong>4</strong>), as well as [HgX<sub>2</sub>{<strong>2</strong>-κ<sup>2</sup><em>Se,N</em><sup><em>py</em></sup>}] (<strong>5</strong>, X = Cl; <strong>6</strong>, X = I) derivatives. Complexes <strong>3</strong>–<strong>6</strong> were isolated and characterized utilizing multinuclear NMR (<sup>1</sup>H, <sup>13</sup>C, and <sup>31</sup>P) and infrared spectroscopy. The molecular structures of compounds <strong>1</strong> and <strong>3</strong>–<strong>6</strong> were elucidated using single-crystal X-ray diffraction analysis. Complexes <strong>3</strong>–<strong>6</strong> constitute the first structurally defined complexes of these ligands with mercury metal identified to date. Dimer <strong>3</strong> is distinguished by the presence of Hg(II) metals exhibiting coordination numbers of five and four inside a single complex.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134810"},"PeriodicalIF":2.1,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144596284","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":"Ball-milling promoted ring-opening selenocyanation of cyclic sulfonium salts with KSeCN","authors":"Sha Peng, Li Tang, Ni-Dan Meng, Han-Yue Peng, Wen-Shi Yao, Shan-Shan Tang, Li-Hua Yang, Long-Yong Xie","doi":"10.1016/j.tet.2025.134816","DOIUrl":"10.1016/j.tet.2025.134816","url":null,"abstract":"<div><div>A sustainable and practical method for ball milling-promoted ring-opening selenocyanation of cyclic sulfonium salts using KSeCN has been developed at room temperature under solvent-free conditions. This approach enables the synthesis of a variety of sulfur-containing selenocyanates, demonstrating a broad substrate scope and compatibility with various functional groups. The short reaction time (10–15 min), along with the absence of catalysts, oxidants, and additives, combined with a straightforward work-up procedure that eliminates the need for extraction, renders this method highly efficient and environmentally friendly.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134816"},"PeriodicalIF":2.1,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614024","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 : 2025-07-08DOI: 10.1016/j.tet.2025.134824
Mariia A. Salykina , Alexander S. Bunev , Natalia A. Lozinskaya , Sergey E. Sosonyuk
{"title":"Bispidine moiety-driven simplified eleutherobin analogues: Synthesis and biological evaluation","authors":"Mariia A. Salykina , Alexander S. Bunev , Natalia A. Lozinskaya , Sergey E. Sosonyuk","doi":"10.1016/j.tet.2025.134824","DOIUrl":"10.1016/j.tet.2025.134824","url":null,"abstract":"<div><div>In the present research, the bispidines were used as a scaffold for the design of new inhibitors of protein-protein interaction with potential antitumor activity. Molecular modeling investigation was performed and optimum symmetrical structures demonstrating strong affinity to the taxane binding site in tubulin were determined. The target structures were analyzed retrosynthetically and produced accordingly. A Mannich-type reaction with urotropine and subsequent ring-opening N-acylation constitute the two key steps in the synthetic pathway. The modification options for C9 position in diazabicyclo[3.3.1]nonanes are discussed. The cytotoxicity of the synthesized bispidine derivatives was evaluated on colon cancer HCT116, pulmonary adenocarcinoma A549 and prostatic adenocarcinoma PC-3 cell lines. Three of the obtained compounds showed cytotoxic activity with IC<sub>50</sub> as low as 7.5–15.6 μM.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134824"},"PeriodicalIF":2.1,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144595499","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":"Hexafluoroisopropanol (HFIP)-mediated catalyst-free microwave-assisted novel multicomponent method to access 3-acyl 1,4-diaryl/alkyl pyrroles","authors":"Manubolu Guravaiah , Gunna Sampurnamma , Thondooru Sruthi , Vinod D. Jadhav , Bandi Ramakrishna , Raju Doddipalla , Satya Rama Krishna Seemakurti , Vidavalur Siddaiah , Katta Venkateswarlu","doi":"10.1016/j.tet.2025.134815","DOIUrl":"10.1016/j.tet.2025.134815","url":null,"abstract":"<div><div>It is becoming increasingly common for synthetic chemists to engage in a variety of synthetic transformations using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), a strong hydrogen bonding-donating, redox-stable polar solvent. Herein, we describe an HFIP-mediated green protocol for the synthesis of novel pyrroles under catalyst-free microwave-assisted conditions. The substituted pyrroles are formed in good to excellent yields (52–99 %) in 1 h from a novel multicomponent reaction of 1-aryl/heteroaryl/alkyl/cycloalkyl substituted 3-(dimethylamino)propenones, aryl/heteroaryl/alkyl/cycloalkyl amines and α-bromo ketones. Furthermore, the structures of products were confirmed by their physical properties, <sup>1</sup>H & <sup>13</sup>C NMR and mass spectral data, and validated by single crystal X-ray diffraction analysis of <strong>4aq</strong> and <strong>4aw</strong>. For the current method, HFIP is recycled and reused. This protocol features catalyst-free conditions, easy recyclability and efficient reusability of HFIP, application of microwaves, ease of handling, short reaction times, high yields of products with vast substrate scope, and preparation of novel pyrroles. This protocol has also been applied for the construction of anticancer agent, 3-aroyl-1,4-diarylpyrrole (ARDAP) (<strong>5</strong>) [with about 8-fold increase of yield and 6.5-fold decrease of time], and a steroid-based complex pyrrole <strong>4bp</strong>.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134815"},"PeriodicalIF":2.1,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614023","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 : 2025-07-08DOI: 10.1016/j.tet.2025.134825
Alexander Baranovsky, Yuri Charnou, Peter Kurman, Siarhei Shepialevich
{"title":"A new route to functionalized nitriles, isoxazolines, isoxazoles and hydroximic acids via nitrile oxide generation from secondary nitro compounds","authors":"Alexander Baranovsky, Yuri Charnou, Peter Kurman, Siarhei Shepialevich","doi":"10.1016/j.tet.2025.134825","DOIUrl":"10.1016/j.tet.2025.134825","url":null,"abstract":"<div><div>Acetylation of 2-nitroalcohols under basic conditions mainly results in the cleavage of the C–C-bond and the formation of nitrile oxide. The nitrile oxide can then be trapped by a dipolarofile, solvent or reducing agent. The procedure leads to the formation of ketonitriles, ω-ketoisoxazolines and ketohydroximic acid derivatives.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134825"},"PeriodicalIF":2.1,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144589288","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":"Synthesis of unsymmetrical urea derivatives via domino ring-opening/Pd-catalyzed decarboxylative cross-coupling reaction of isatin-3-oxime and isocyanide","authors":"Pooja Soam, Kirti Singh, Parmjeet Kaur, Vikas Tyagi","doi":"10.1016/j.tet.2025.134809","DOIUrl":"10.1016/j.tet.2025.134809","url":null,"abstract":"<div><div>This study presents a novel palladium-catalyzed method to efficiently synthesize unsymmetrical urea derivatives by domino ring-opening and decarboxylative cross-coupling involving isatin-3-oxime with isocyanides. The optimized protocol demonstrates excellent substrate compatibility, yielding a broad array of urea derivatives in moderate to good yields. A plausible reaction mechanism is proposed which was investigated using various control experiments that revealed key roles of palladium catalysis, offering insights into the ring-opening and decarboxylative coupling steps along with the necessity of free N–H functionality on isatin-3-oxime. Moreover, the synthesized derivatives were further transformed into quinazolinone heterocycles, underscoring their synthetic versatility.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134809"},"PeriodicalIF":2.1,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144589171","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 : 2025-07-07DOI: 10.1016/j.tet.2025.134812
Ying Fan , Ruikang Wang , Gaowang Yang , Peng Jin , Zuyu Bai , Ke-Hu Wang , Danfeng Huang , Yulai Hu
{"title":"[3+2]-cycloaddition reactions of α-trifluoromethyl imino esters with nitrile Imines: Construction of penta-substituted 5-CF3-1,2,4-triazolines","authors":"Ying Fan , Ruikang Wang , Gaowang Yang , Peng Jin , Zuyu Bai , Ke-Hu Wang , Danfeng Huang , Yulai Hu","doi":"10.1016/j.tet.2025.134812","DOIUrl":"10.1016/j.tet.2025.134812","url":null,"abstract":"<div><div>An efficient [3 + 2]-cycloaddition reaction between <em>α</em>-trifluoromethyl imino esters and di/trifluoromethyl nitrile imines or nonfluorinated nitrile imines generated <em>in-situ</em> from hydrazonoyl halides in the presence of base has been investigated, affording a series of fluoroalkylated penta-substituted 1,2,4-triazolines with a quaternary C5 carbon atom in high yields with excellent regioselectivity under mild conditions. The results show that <em>α</em>-trifluoromethyl imino esters could serve as outstanding dipolarophiles suitable for [3 + 2]-cycloadditions with various fluorinated or non-fluorinated nitrile imines.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134812"},"PeriodicalIF":2.1,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144579463","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 : 2025-07-05DOI: 10.1016/j.tet.2025.134811
Jiao Wang, Botao Wang, Ting Shao, Zheng Li
{"title":"One-pot three-component construction of benzo[4,5]imidazo[1,2-a]benzo[4,5]thieno[3,2-d]pyrimidines through [5+1+3] cascade cyclization","authors":"Jiao Wang, Botao Wang, Ting Shao, Zheng Li","doi":"10.1016/j.tet.2025.134811","DOIUrl":"10.1016/j.tet.2025.134811","url":null,"abstract":"<div><div>A one-pot three-component method for the effective construction of 12-arylbenzo[4,5]imidazo[1,2-<em>a</em>]benzo[4,5]thieno[3,2-<em>d</em>]pyrimidines through [5 + 1+3] cascade cyclization of <em>o</em>-nitrochalcones, 2-aminobenzimidazoles, and elemental sulfur is described. The target products are synthesized through the simultaneous formation of two C–S bonds and two C–N bonds. The salient features of this protocol are the use of commercially available starting materials and inexpensive and easy-to-handle solid sulfur source, transition-metal-free condition, wide substrate scope, high yield, and simple workup procedures. The method can also be extended to the synthesis of gram scale.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134811"},"PeriodicalIF":2.1,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144563058","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 : 2025-07-05DOI: 10.1016/j.tet.2025.134803
Vishwa K. Patel, Divyani P. Patel, Satish Kumar Singh
{"title":"The photocatalytic journey of heteroatoms: Illuminating aza-Henry reactions in organic synthesis","authors":"Vishwa K. Patel, Divyani P. Patel, Satish Kumar Singh","doi":"10.1016/j.tet.2025.134803","DOIUrl":"10.1016/j.tet.2025.134803","url":null,"abstract":"<div><div>Heteroatoms play a critical role in synthetic chemistry and the development of organic materials, significantly influencing molecular structure and reactivity. This review highlights the pivotal role of heteroatoms in synthetic chemistry and organic materials, with a specific focus on advancements in photocatalyzed aza-Henry reaction in the formation of <em>β</em>-nitroamine compounds. This study emphasizes the aza-Henry reaction, a highly adaptable approach for the synthesis of <em>β</em>-nitroamine compounds, which serve as crucial intermediates in both medicinal and synthetic chemistry. Their unique electronic and steric properties allow for the construction of innovative reagents, catalysts, and materials with applications spanning pharmaceuticals, polymers, and photochemistry. Special attention is given to the role of visible light and heteroatom catalysts in the synthesis of complex nitrogen-containing compounds. This strategy avoids harsh reaction conditions and expands the substrate scope and selectivity by utilizing heteroatom catalysts in conjunction with visible-light activation, offering a sustainable and efficient strategy for the synthesis of structurally diverse <em>β</em>-nitroamine compounds. This approach not only broadens substrate scope but also enhances reaction selectivity, reinforcing its significance in complex molecule synthesis under environmentally benign conditions.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134803"},"PeriodicalIF":2.1,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144579462","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 : 2025-07-05DOI: 10.1016/j.tet.2025.134808
Yuanwei You , Fei Tan , Zhijian Luo , Ting Peng , Yujiao He , Chunran Zhang , Yuchi Wang , Hongbo Dong
{"title":"Total Synthesis and Reconfirmation of the Absolute Configuration of Melanochromone","authors":"Yuanwei You , Fei Tan , Zhijian Luo , Ting Peng , Yujiao He , Chunran Zhang , Yuchi Wang , Hongbo Dong","doi":"10.1016/j.tet.2025.134808","DOIUrl":"10.1016/j.tet.2025.134808","url":null,"abstract":"<div><div>Herein, we present the first regioselective total synthesis of the natural chromone (3’<em>R</em>)-melanochromone (<strong>2</strong>), along with its enantiomer (3’<em>S</em>)-melanochromone (<strong>1</strong>), and the structurally related chromones greveichromenol (<strong>3</strong>) and ledebouriellol (<strong>4</strong>). The synthesis was accomplished using the readily available trihydroxyacetophenone as the starting material and the well-established Jacobson’s asymmetric epoxidation method. Although chromones <strong>1</strong>-<strong>4</strong> did not demonstrate significant anti-inflammatory activity, our synthetic approach provides a viable strategy for further exploration of this class of natural chromones.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"185 ","pages":"Article 134808"},"PeriodicalIF":2.1,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144563057","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}