Tetrahedron最新文献

{"title":"Visible-light-enabled CuCl2-mediated tandem C(sp3)-H and C(sp3)-O oxidant/bisindolylation of ethers – Synthesis of bisindolylmethane derivatives","authors":"Chenglei Yang,&nbsp;Xiaotao Qin,&nbsp;Jinkai Hu,&nbsp;Bosen Wang,&nbsp;Jinhui Yang,&nbsp;Dianjun Li","doi":"10.1016/j.tet.2025.134949","DOIUrl":"10.1016/j.tet.2025.134949","url":null,"abstract":"<div><div>Under the participation of cheap and readily available CuCl₂, a visible light-induced tandem C(sp³)-H oxidation, C(sp³)-O cleavage and Friedel−Crafts alkylation of indoles and aliphatic ethers in the absence of ligand and oxidants is developed, affording synthetically useful 3,3′-bisindolylmethane derivatives in moderate to good yields. This transformation exhibits broad substrate scope and good functional group compatibility.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"188 ","pages":"Article 134949"},"PeriodicalIF":2.2,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227820","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":"Substituent-dependent synthesis of isomeric imidazoles from azirines and amidines","authors":"Ekaterina E. Galenko,&nbsp;Irina N. Prokop'eva,&nbsp;Alexander Yu. Ivanov,&nbsp;Timur O. Zanakhov,&nbsp;Mikhail S. Novikov,&nbsp;Alexander F. Khlebnikov","doi":"10.1016/j.tet.2025.134950","DOIUrl":"10.1016/j.tet.2025.134950","url":null,"abstract":"<div><div>The synthesis of 2,4,5-trisubstituted imidazoles with a Weinreb amide, ester, keto or aldehyde group, as well as 2,5-diaryl substituted imidazoles by the reaction of amidines with azirines has been reported. The reaction mechanism explaining dependence of imidazole structure on substituent at the position 2 of the azirine is discussed based on experiment with ¹⁵N-labelled azirine and DFT calculations.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"188 ","pages":"Article 134950"},"PeriodicalIF":2.2,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227816","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":"Mechanistic insights into intramolecular carbon–carbon bond formation and carbon–boron cyclization of non-conjugated terminal diacetylenes by frustrated Lewis Pairs: A DFT study","authors":"Tulsi R. Patel ,&nbsp;Bishwajit Ganguly","doi":"10.1016/j.tet.2025.134948","DOIUrl":"10.1016/j.tet.2025.134948","url":null,"abstract":"<div><div>Frustrated Lewis pairs (FLPs) exhibit highly variable reactivity with non-conjugated terminal diacetylenes, leading to 1,2-<em>anti-</em>addition products and also to intramolecular C-C coupling followed by C-B cyclization with the variation in the Lewis bases. However, the detailed mechanisms of such reactions have not been examined. This study reports a detailed mechanistic investigation of C-C coupling followed by C-B cyclization of 1,6-heptadiyne by FLPs. Density functional theory calculations unveil three different mechanistic pathways, including 1,1-carboboration, and two alternative variations of 1,2-carboboration pathways. The 1,1-carboboration involves C-C coupling on geminal carbon [pathway (a)], while 1,2-carboboration involves vicinal C-C coupling [pathways (b) and (c)]. The computed results reveal that the 1,1-carboboration is energetically favoured and the formation of regioselective 8-membered product is governed by the kinetic effect in the reaction. The role of different Lewis bases (PPh₂[C₆H₃(CF₃)₂) and linkers [di(propargyl)ether] suggests the ease to form the 8-membered zwitterionic heterocyclic products via 1,1-carboboration pathway.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"188 ","pages":"Article 134948"},"PeriodicalIF":2.2,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145157089","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":"DFT study on Ni–C bond dissociation enthalpies of nickel-carbon complexes in photoredox/nickel dual catalysis C(sp2)-C(sp3) coupling reactions","authors":"Qianxi Zhang,&nbsp;Wenrui Zheng,&nbsp;Mengtong Shi,&nbsp;Hao Jin","doi":"10.1016/j.tet.2025.134938","DOIUrl":"10.1016/j.tet.2025.134938","url":null,"abstract":"<div><div>Traditional transition metal catalysis efficiently forms C(sp²)-C(sp²) bonds, but C(sp²)-C(sp³) couplings remain challenging due to sluggish C(sp³) oxidative addition and metalation, and the propensity for β-hydride elimination. A notable advancement is the development of dual catalytic platforms that synergistically integrate transition metal catalysts with photoredox catalysts, offering a powerful strategy for constructing challenging C(sp²)-C(sp³) linkages. Nickel complexes, recognized for their cost-effectiveness, earth-abundant nature, and catalytic efficiency, have emerged as pivotal players in this field. Their compatibility with photoredox catalysis enables a unique mechanistic pathway where nickel intermediates coordinate with (hetero)aryl halides or alkyl radicals, forming critical Ni–C bonds during the reaction cycle. Accurately quantifying the strength of these Ni–C bonds through homolytic bond dissociation enthalpy (BDE) measurements hold critical importance for understanding catalytic behavior. In this study, we systematically evaluated 14 nickel-carbon complexes using ten density functional theory (DFT) methodologies, benchmarking calculated BDE values against experimental data. The M06 functional outperformed others, exhibiting the lowest root-mean-square error (RMSE) of 2.7 kcal/mol. Leveraging this finding, the M06 functional was applied to evaluate Ni–C BDEs in model complexes I and II under Ni/photoredox dual catalytic conditions, while probing substituent effects. Supplementary investigations, natural bond orbital (NBO) analyses and frontier molecular orbital energy assessments, were conducted to further understand the variation patterns of Ni–C BDE. Transition state characterization further uncovered a direct correlation between Ni–C bond strength and activation free energies, establishing a structure-activity framework that links thermodynamic stability with mechanistic feasibility.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134938"},"PeriodicalIF":2.2,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105728","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":"High efficient synthesis of HMX from DPT using deep eutectic catalyst","authors":"Jianjian Hu ,&nbsp;Dapeng Jiang ,&nbsp;Yujie Huang ,&nbsp;Xixue Liu ,&nbsp;Shenyuan Gao ,&nbsp;Kejun Wu ,&nbsp;Chaohong He ,&nbsp;Liyan Dai","doi":"10.1016/j.tet.2025.134936","DOIUrl":"10.1016/j.tet.2025.134936","url":null,"abstract":"<div><div>A deep eutectic catalyst (DEC) catalyzed nitration reaction for synthesizing 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) from 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT) has been developed, using a reduced amount of fuming nitric acid and achieving a maximum yield of 85.8 %. In addition, the introduction of DEC significantly enhanced the nitration efficiency of nitrogen-containing substrates such as dimorpholinomethane and dipiperidinomethane, notably increasing the yields of their corresponding nitroso products. This method provides a greener and more economical alternative to ionic liquid-based processes.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134936"},"PeriodicalIF":2.2,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118236","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 1,3-dialkylthioselenoglycolurils - novel antifungal agents","authors":"Vladimir V. Baranov ,&nbsp;Anton A. Galochkin ,&nbsp;Anna L. Alekseenko ,&nbsp;Sergei V. Popkov ,&nbsp;Natalya G. Kolotyrkina ,&nbsp;Yulia V. Nelyubina ,&nbsp;Anastasiya A. Globa ,&nbsp;Angelina N. Kravchenko ,&nbsp;Leonid L. Fershtat","doi":"10.1016/j.tet.2025.134947","DOIUrl":"10.1016/j.tet.2025.134947","url":null,"abstract":"<div><div>A two-step synthesis of pharmacologically relevant 1,3-dialkyl-5-selenoxohexahydroimidazo[4,5-<em>d</em>]imidazole-2(1<em>H</em>)-thiones (thioselenoglycolurils) starting from readily available thioglycolurils was realized for the first time. The developed protocol involves <em>S</em>-methylation of initial thioglycolurils followed by selenation of thus formed isothiouronium salts with NaHSe generated <em>in situ</em> from grey Se and NaBH₄. <em>In vitro</em> study of antifungal activity against <em>Sclerotinia sclerotiorum</em>, <em>Fusarium oxysporum</em>, <em>Fusarium maniliforme</em>, <em>Bipolaris sorokiniana</em>, <em>Venturia inaequalis</em>, <em>Rhizoctonia solani</em> phytopathogens and yeasts <em>Candida albicans</em> and <em>Cryptococcus neoformans</em>, <em>Candida auris,</em> MDR <em>Candida auris, Candida glabrata</em> was performed. It was found that 8 thioselenoglycolurils completely inhibited the growth of <em>V</em>. <em>inaequalis</em> and <em>R</em>. <em>solani</em> fungi and partially suppress the growth of <em>B</em>. <em>sorokiniana</em> fungus (MGI 59–67 %) analogous to triadimefon (MGI 68 %). Effective antifungal action towards <em>C. albicans</em> and <em>C. neoformans</em> (MIC <span><math><mrow><mo>≤</mo></mrow></math></span> 0.25 μg/mL) with no discernible toxicity against mamallian cells was revealed for 4 representatives of thioselenoglycolurils. Effective growth inhibition of gram-positive bacterium <em>S. aureus</em>, yeast <em>C. neoformans, C. auris,</em> MDR <em>C. auris, C. glabrata</em> was additionally noted for 1,3-diethylthioselenoglycoluril. Moreover, the latter compound has low toxicity (LD₅₀ = 129 mg/kg) and can be referred to as a lead candidate for the development of new antifungal pharmaceuticals.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134947"},"PeriodicalIF":2.2,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105722","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 colorimetric/fluorescent dual-mode probe for real-time hydrazine detection in biological, food, and environmental samples","authors":"Yun Bian ,&nbsp;Xuan Zhao ,&nbsp;Wenmeng He ,&nbsp;Wei Zhao ,&nbsp;Beibei Wang","doi":"10.1016/j.tet.2025.134945","DOIUrl":"10.1016/j.tet.2025.134945","url":null,"abstract":"<div><div>Hydrazine (N₂H₄), a pivotal chemical material, poses significant environmental and health risks. Accurate risk assessment necessitates highly sensitive detection methods. To address this, we introduce TPS, an innovative colorimetric/fluorescent dual-mode probe based on the triphenylamine derivative as electron-donating group and thiobarbituric acid as electron-withdrawing group, specifically designed for N₂H₄ detection in environmental and biological matrices. <strong>TPS</strong> exhibits exceptional sensitivity(detection limit:12 nM), rapid response (5 s) and stability across a broad pH range (6–10). Furthermore, we developed a smartphone-integrated sensing platform coupled with <strong>TPS</strong>-embedded test strips, enabling on-site, real-time monitoring of N₂H₄ in gaseous and aqueous phase. Critically, <strong>TPS</strong> successfully monitored N₂H₄ in diverse biological systems including living cells, bacteria, <em>Arabidopsis thaliana</em>, onion epidermal cells, rose petals and food samples. This work not only presents a versatile tool for N₂H₄ surveillance across multiple contexts but also paves the way for new research avenues in chemical sensing and environmental health.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134945"},"PeriodicalIF":2.2,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061049","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":"Amidation of amino aryl acids with orthoesters in aqueous ammonium hydroxide: A strategy to construct quinazolinones and pyrido[2,3-d]pyrimidinones","authors":"Subrata Barick,&nbsp;Sandeep Chandrashekharappa","doi":"10.1016/j.tet.2025.134940","DOIUrl":"10.1016/j.tet.2025.134940","url":null,"abstract":"<div><div>A one-pot oxidative cyclization of 2-amino aryl acids with orthoesters to quinazoline-4(3<em>H</em>)-ones and pyrido[2,3-<em>d</em>]pyrimidinones was described in a greener approach using aqueous ammonium hydroxide. The synthetic protocol enables greater selectivity with synthetic utility. A wide range of substrate scope was explored with good to excellent yields. The reaction mechanism involves <em>N</em>-benzylation/alkylation, amidation, and subsequent oxidative annulation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134940"},"PeriodicalIF":2.2,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105724","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":"Cobalt-catalyzed alkene hydrohalogenation via hydrogen atom transfer","authors":"Arman Khosravi,&nbsp;Ming-Yu Ngai","doi":"10.1016/j.tet.2025.134944","DOIUrl":"10.1016/j.tet.2025.134944","url":null,"abstract":"<div><div>Alkene hydrohalogenation is a fundamental transformation for the synthesis of organohalides, key intermediates in organic synthesis, pharmaceuticals, and materials science. Traditional ionic methods with hydrogen halides are limited by harsh conditions, poor functional group tolerance, and regioselectivity issues. Recently, cobalt-catalyzed hydrohalogenation via metal-hydride hydrogen atom transfer (MHAT) has emerged as a versatile and radical-based alternative, enabling mild conditions, broad functional group tolerance, and tunable regioselectivity. This mini-review provides a comprehensive overview of the development in cobalt-catalyzed alkene hydrohalogenation via MHAT, with particular emphasis on methodological innovations, substrate scopes, mechanistic principles, and emerging applications. The continued growth of this field is poised to expand the synthetic utility and sustainability of alkene hydrofunctionalization, opening new avenues for programmable C–X bond formation across diverse chemical contexts.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134944"},"PeriodicalIF":2.2,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105730","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":"N6-α-azidoacetyl sydnone imines: Synthesis and reactivity in azide-alkyne cycloaddition reactions","authors":"Natalia V. Kalganova ,&nbsp;Ivan A. Platonov ,&nbsp;Alexander F. Smol'yakov ,&nbsp;Ivan A. Godovikov ,&nbsp;Ilya A. Cherepanov","doi":"10.1016/j.tet.2025.134946","DOIUrl":"10.1016/j.tet.2025.134946","url":null,"abstract":"<div><div>A convenient preparative method for the synthesis of previously unknown <em>N</em>₆-α-azidoacetyl sydnone imines was developed, and their reactivity in azide – alkyne cycloaddition reactions was investigated. Based on CuAAC reactions, sydnone imine conjugates with protected glucose, isocoumarin, and a lipoic acid residue were synthesized.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"187 ","pages":"Article 134946"},"PeriodicalIF":2.2,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105726","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}