Pub Date : 2026-03-01Epub Date: 2025-12-13DOI: 10.1016/j.tet.2025.135099
Aigui Zhang, Wenjing Luo, Zhonghua Qu, Weiqing Yang, Min Luo, Xin Li, Menglin Ma
N-Aryl-1,2,3-triazole compounds are important pharmaceutical motifs synthesized via nucleophile reactions with triazoles. Typically, both N2 and N1 regioisomers are produced simultaneously. In this article, a synergistic catalytic system comprising CuI and 1,2-diphenylethylenediamine (DPEN) was employed for the selective N2-coupling of 2-bromobenzoic acid with triazole. This reaction yielded 2-(2H-1,2,3-triazol-2-yl)benzoic acid (4a) with an impressive yield of 86 % and a regioselectivity of 91 % for the N2 isomer. Additionally, 2-bromobenzoic acid served as a cost-effective alternative to the traditionally used 2-iodobenzoic acid; notably, the reaction time was reduced from 4 h to 1.5 h. Mechanistic studies indicated that the DPEN ligand promotes carbon-copper bond formation, enhancing reaction activity and accelerating the overall rate; However, while there has been some improvement in N2 selectivity, it remains less than ideal.
n -芳基-1,2,3-三唑化合物是与三唑通过亲核反应合成的重要药物基序。通常，N2和N1区域异构体同时产生。本文采用由CuI和1,2-二苯乙二胺（DPEN）组成的协同催化体系进行了2-溴苯甲酸与三唑的选择性n2偶联反应。该反应生成2-（2h -1,2,3-三唑-2-基）苯甲酸（4a），其N2异构体的产率为86%，区域选择性为91%。此外，2-溴苯甲酸作为传统上使用的2-碘苯甲酸的一种具有成本效益的替代品；反应时间由4 h缩短至1.5 h。机理研究表明，DPEN配体促进了碳铜键的形成，提高了反应活性，加快了反应的总速率；然而，虽然对N2的选择性有了一定的提高，但仍然不够理想。
{"title":"Investigation of the N2-Selective functionalization reaction of 2H-1,2,3-triazole catalyzed by a synergistic combination of copper and diamine ligands","authors":"Aigui Zhang, Wenjing Luo, Zhonghua Qu, Weiqing Yang, Min Luo, Xin Li, Menglin Ma","doi":"10.1016/j.tet.2025.135099","DOIUrl":"10.1016/j.tet.2025.135099","url":null,"abstract":"<div><div><em>N</em>-Aryl-1,2,3-triazole compounds are important pharmaceutical motifs synthesized via nucleophile reactions with triazoles. Typically, both <em>N</em><sup><em>2</em></sup> and <em>N</em><sup><em>1</em></sup> regioisomers are produced simultaneously. In this article, a synergistic catalytic system comprising CuI and 1,2-diphenylethylenediamine (DPEN) was employed for the selective <em>N</em><sup><em>2</em></sup>-coupling of 2-bromobenzoic acid with triazole. This reaction yielded 2-(2<em>H</em>-1,2,3-triazol-2-yl)benzoic acid (<strong>4a</strong>) with an impressive yield of 86 % and a regioselectivity of 91 % for the <em>N</em><sup><em>2</em></sup> isomer. Additionally, 2-bromobenzoic acid served as a cost-effective alternative to the traditionally used 2-iodobenzoic acid; notably, the reaction time was reduced from 4 h to 1.5 h. Mechanistic studies indicated that the DPEN ligand promotes carbon-copper bond formation, enhancing reaction activity and accelerating the overall rate; However, while there has been some improvement in <em>N</em><sup><em>2</em></sup> selectivity, it remains less than ideal.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135099"},"PeriodicalIF":2.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786966","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 : 2026-03-01Epub Date: 2025-12-14DOI: 10.1016/j.tet.2025.135100
Shenao Qu , Yue Wang , Er-Qing Li
In this work, we report the phosphine-catalyzed [4 + 2] cycloaddition reaction between benzofuran-derived azadienes and conjugated dienes. This method provides an efficient approach for constructing benzofuran-fused nitrogen-containing heterocyclic skeletons. The reaction features unique regioselectivity, good yields, excellent diastereoselectivity and broad substrate scope. Moreover, the potential synthetic utility of this strategy is demonstrated through gram-scale experiment and subsequent synthetic transformation.
{"title":"Phosphine-catalyzed [4 + 2] cycloaddition of benzofuran-derived azadienes and conjugated dienes: Synthesis of 1,2,3,4-tetrahydrobenzofuro[3,2-b]pyridines","authors":"Shenao Qu , Yue Wang , Er-Qing Li","doi":"10.1016/j.tet.2025.135100","DOIUrl":"10.1016/j.tet.2025.135100","url":null,"abstract":"<div><div>In this work, we report the phosphine-catalyzed [4 + 2] cycloaddition reaction between benzofuran-derived azadienes and conjugated dienes. This method provides an efficient approach for constructing benzofuran-fused nitrogen-containing heterocyclic skeletons. The reaction features unique regioselectivity, good yields, excellent diastereoselectivity and broad substrate scope. Moreover, the potential synthetic utility of this strategy is demonstrated through gram-scale experiment and subsequent synthetic transformation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135100"},"PeriodicalIF":2.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786971","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 : 2026-03-01Epub Date: 2025-12-11DOI: 10.1016/j.tet.2025.135090
Divyani P. Patel, Vishwa K. Patel, Satish Kumar Singh
Vinyl sulfones are valued for their unique chemical properties and bioactivity, but creating a wide range of different analogs remains a challenge. To address this limitation, we have developed a novel and eco-friendly method for the synthesis of (E)-vinyl sulfones via visible light-mediated deborative sulfonylation of alkenyl boronic acids with sulfonyl hydrazides. Our straightforward and metal-free sulfonylation utilises eco-friendly visible light irradiation, and rose bengal organic dye, while a water-ethanol mixture serves as a green solvent, removing the necessity for external oxidants. The reaction delivers (E)-vinyl sulfones in good to excellent yields within a short reaction time and exhibits broad substrate scope with excellent functional group tolerance, including electron-rich, electron-poor, as well as aliphatic, heteroaryl, and sterically hindered substituent derivatives. Mechanistic investigations support a photoredox single-electron transfer (SET) pathway involving sulfonyl radicals. This mild and environmentally friendly protocol provides a valuable approach for the synthesis of bioactive (E)-vinyl sulfones, which are key structural motifs in pharmaceuticals, agrochemicals, and material science.
{"title":"Photocatalytic deborative sulfonylation of alkenyl boronic acids with sulfonyl hydrazides under green environmental conditions","authors":"Divyani P. Patel, Vishwa K. Patel, Satish Kumar Singh","doi":"10.1016/j.tet.2025.135090","DOIUrl":"10.1016/j.tet.2025.135090","url":null,"abstract":"<div><div>Vinyl sulfones are valued for their unique chemical properties and bioactivity, but creating a wide range of different analogs remains a challenge. To address this limitation, we have developed a novel and eco-friendly method for the synthesis of (<em>E</em>)-vinyl sulfones <em>via</em> visible light-mediated deborative sulfonylation of alkenyl boronic acids with sulfonyl hydrazides. Our straightforward and metal-free sulfonylation utilises eco-friendly visible light irradiation, and rose bengal organic dye, while a water-ethanol mixture serves as a green solvent, removing the necessity for external oxidants. The reaction delivers (<em>E</em>)-vinyl sulfones in good to excellent yields within a short reaction time and exhibits broad substrate scope with excellent functional group tolerance, including electron-rich, electron-poor, as well as aliphatic, heteroaryl, and sterically hindered substituent derivatives. Mechanistic investigations support a photoredox single-electron transfer (SET) pathway involving sulfonyl radicals. This mild and environmentally friendly protocol provides a valuable approach for the synthesis of bioactive (<em>E</em>)-vinyl sulfones, which are key structural motifs in pharmaceuticals, agrochemicals, and material science.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"191 ","pages":"Article 135090"},"PeriodicalIF":2.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786973","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 : 2026-01-15Epub Date: 2025-11-15DOI: 10.1016/j.tet.2025.135065
Aniket Majhi, Samim Sahaji, Anup Kumar Misra
A straightforward synthetic strategy has been developed for the synthesis of the tetrasaccharide containing a β-d-mannose moiety corresponding to the O-specific polysaccharide of Salmonella cerro (S. cerro) O:18 strain. The synthetic strategy involves 1,2-cis glycosylation of a d-mannose unit by H-bond mediated aglycone delivery using judiciously functionalized d-mannose thioglycoside donor. The glycosylation steps were high yielding with satisfactory stereochemistry at the glycosyl linkages.
采用一种简单的合成策略，合成了含有β-d-甘露糖片段的四糖，该四糖片段与沙门氏菌cerro (S. cerro) O:18菌株的O特异性多糖相对应。该合成策略包括利用合理功能化的d-甘露糖硫苷供体，通过氢键介导的苷元传递，将d-甘露糖单元1,2-顺式糖基化。糖基化步骤产率高，在糖基键上具有令人满意的立体化学性质。
{"title":"Synthesis of the β-d-mannose containing tetrasaccharide repeating unit corresponding to the O-specific polysaccharide of Salmonella cerro O:18","authors":"Aniket Majhi, Samim Sahaji, Anup Kumar Misra","doi":"10.1016/j.tet.2025.135065","DOIUrl":"10.1016/j.tet.2025.135065","url":null,"abstract":"<div><div>A straightforward synthetic strategy has been developed for the synthesis of the tetrasaccharide containing a β-<span>d</span>-mannose moiety corresponding to the <em>O</em>-specific polysaccharide of <em>Salmonella cerro</em> (<em>S. cerro</em>) O:18 strain. The synthetic strategy involves 1,2-<em>cis</em> glycosylation of a <span>d</span>-mannose unit by <em>H</em>-bond mediated aglycone delivery using judiciously functionalized <span>d</span>-mannose thioglycoside donor. The glycosylation steps were high yielding with satisfactory stereochemistry at the glycosyl linkages.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135065"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577162","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 : 2026-01-15Epub Date: 2025-10-27DOI: 10.1016/j.tet.2025.135025
YunXia Yang, Xingang Xie, Xuegong She
In recent years, cage-like compounds have attracted extensive attention in chemistry, biology and drug discovery due to their unique spatial structures and remarkable bioactive properties. This paper systematically reviewed the structurally diverse cage-like sesquiterpenoids discovered and isolated from natural drug resources during the 2017–2025 period, focusing on their novel backbone features, extensive bioactivity profiles, and in-depth discussion of the latest advances in their total synthetic works. By analyzing the construction strategies and methodologies for these complex molecules, we aimed to provide some perspective theoretical insights and practical guidance for the total synthesis of this type of intricate natural products.
{"title":"Recent advances in total syntheses of cage-like sesquiterpenoids","authors":"YunXia Yang, Xingang Xie, Xuegong She","doi":"10.1016/j.tet.2025.135025","DOIUrl":"10.1016/j.tet.2025.135025","url":null,"abstract":"<div><div>In recent years, cage-like compounds have attracted extensive attention in chemistry, biology and drug discovery due to their unique spatial structures and remarkable bioactive properties. This paper systematically reviewed the structurally diverse cage-like sesquiterpenoids discovered and isolated from natural drug resources during the 2017–2025 period, focusing on their novel backbone features, extensive bioactivity profiles, and in-depth discussion of the latest advances in their total synthetic works. By analyzing the construction strategies and methodologies for these complex molecules, we aimed to provide some perspective theoretical insights and practical guidance for the total synthesis of this type of intricate natural products.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135025"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145384503","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 : 2026-01-15Epub Date: 2025-10-30DOI: 10.1016/j.tet.2025.135039
Jia-Le Fu , Jia-Lun Luo , Xue-Feng Zhao , Dan Zhang , Tao Wu , Hongwei Si , Peng-Fei Dai
The oxidation of aldehydes to corresponding carboxylic acids catalyzed by tetra-n-butylammonium decatungstate (TBADT) under visible light in CH3CN or H2O have been realized for the first time. Mono-aldehydes and dialdehydes, especially aldehydes bearing with electron-withdrawing groups (e.g.: –NO2, –CO2R, –CHO, –COR, –CN, –CF3, etc.) and vulnerable groups (e.g.: –OH, -SMe, etc.) are well compatible with in moderate to good yields. And detailed mechanistic investigations have revealed the catalytic role of TBADT in the oxidation. A gram-scale synthesis has been implemented with a gas-liquid flow reaction model. Meanwhile, economical and environmentally friendly reagents make this transformation more possible for the industrial applications.
{"title":"Visible-light catalytic aerobic oxidation of aldehydes","authors":"Jia-Le Fu , Jia-Lun Luo , Xue-Feng Zhao , Dan Zhang , Tao Wu , Hongwei Si , Peng-Fei Dai","doi":"10.1016/j.tet.2025.135039","DOIUrl":"10.1016/j.tet.2025.135039","url":null,"abstract":"<div><div>The oxidation of aldehydes to corresponding carboxylic acids catalyzed by tetra-<em>n</em>-butylammonium decatungstate (TBADT) under visible light in CH<sub>3</sub>CN or H<sub>2</sub>O have been realized for the first time. Mono-aldehydes and dialdehydes, especially aldehydes bearing with electron-withdrawing groups (e.g.: –NO<sub>2</sub>, –CO<sub>2</sub>R, –CHO, –COR, –CN, –CF<sub>3</sub>, etc.) and vulnerable groups (e.g.: –OH, -SMe, etc.) are well compatible with in moderate to good yields. And detailed mechanistic investigations have revealed the catalytic role of TBADT in the oxidation. A gram-scale synthesis has been implemented with a gas-liquid flow reaction model. Meanwhile, economical and environmentally friendly reagents make this transformation more possible for the industrial applications.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135039"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415117","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 : 2026-01-15Epub Date: 2025-11-07DOI: 10.1016/j.tet.2025.135044
Shikai Yang , Ziyan Wu , Xindi Li , Jinshan Li , Hongtao Liu , Juanzu Liu , Chunman Jia
A simple and practical synthetic route for the scalable synthesis of highly valuable α-trifluoromethylated indole-3-carbinols with more cost-effective trifluoroacetaldehyde hydrate has been developed. This convenient recyclable H-bonding HFIP-promoted synthetic protocol allows the rapid construction of structurally diverse α-trifluoromethylated indole-3-carbinols with high efficiency. The synthetic utility of this protocol is further highlighted by the decagram-scale synthesis and product derivatizations.
{"title":"A practical and scalable synthetic protocol for α-trifluoromethylated indole-3-carbinols","authors":"Shikai Yang , Ziyan Wu , Xindi Li , Jinshan Li , Hongtao Liu , Juanzu Liu , Chunman Jia","doi":"10.1016/j.tet.2025.135044","DOIUrl":"10.1016/j.tet.2025.135044","url":null,"abstract":"<div><div>A simple and practical synthetic route for the scalable synthesis of highly valuable α-trifluoromethylated indole-3-carbinols with more cost-effective trifluoroacetaldehyde hydrate has been developed. This convenient recyclable H-bonding HFIP-promoted synthetic protocol allows the rapid construction of structurally diverse α-trifluoromethylated indole-3-carbinols with high efficiency. The synthetic utility of this protocol is further highlighted by the decagram-scale synthesis and product derivatizations.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135044"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475102","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 : 2026-01-15Epub Date: 2025-10-30DOI: 10.1016/j.tet.2025.135029
Olajide B. Omoyeni , Temitope O. Olomola , Nusrat O. Omisore , Taiwo F. Ojo , Craig A. Obafemi
A series of eight spirocyclic oxindole derivatives 1a–1d, 2a–2d was synthesized according to established methods; this included the previously unreported compound, 2c. The structures of all compounds were unequivocally characterised by spectroscopic analysis (IR, 1H NMR, 13C NMR) and high-resolution mass spectrometry (HRMS). The in vitro antibacterial activity was assessed against representative Gram-positive (Bacillus subtilis, Bacillus anthracis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa) bacterial strains by determining the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). The compounds exhibited a range of bactericidal effects. Notably, derivative 2c demonstrated potent, broad-spectrum activity against B. subtilis, B. anthracis, and E. coli. Furthermore, both 2b and 2c exhibited significant efficacy against a clinically resistant strain of P. aeruginosa. In contrast, compounds 1a and 1d showed negligible antibacterial activity. These results underscore the potential of the spirocyclic oxindole scaffold in the development of novel antibacterial agents. This study provides a foundation for future work to optimize the structure-activity relationship and elucidate the precise mechanism of action of these compounds.
{"title":"Exploring the antibacterial potential of spirocyclic oxindole derivatives: Synthesis and biological evaluation","authors":"Olajide B. Omoyeni , Temitope O. Olomola , Nusrat O. Omisore , Taiwo F. Ojo , Craig A. Obafemi","doi":"10.1016/j.tet.2025.135029","DOIUrl":"10.1016/j.tet.2025.135029","url":null,"abstract":"<div><div>A series of eight spirocyclic oxindole derivatives <strong>1a–1d</strong>, <strong>2a–2d</strong> was synthesized according to established methods; this included the previously unreported compound, <strong>2c</strong>. The structures of all compounds were unequivocally characterised by spectroscopic analysis (IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR) and high-resolution mass spectrometry (HRMS). The in vitro antibacterial activity was assessed against representative Gram-positive (<em>Bacillus subtilis</em>, <em>Bacillus anthracis</em>) and Gram-negative (<em>Escherichia coli</em>, <em>Pseudomonas aeruginosa</em>) bacterial strains by determining the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). The compounds exhibited a range of bactericidal effects. Notably, derivative <strong>2c</strong> demonstrated potent, broad-spectrum activity against <em>B. subtilis</em>, <em>B. anthracis</em>, and <em>E. coli</em>. Furthermore, both <strong>2b</strong> and <strong>2c</strong> exhibited significant efficacy against a clinically resistant strain of <em>P. aeruginosa</em>. In contrast, compounds <strong>1a</strong> and <strong>1d</strong> showed negligible antibacterial activity. These results underscore the potential of the spirocyclic oxindole scaffold in the development of novel antibacterial agents. This study provides a foundation for future work to optimize the structure-activity relationship and elucidate the precise mechanism of action of these compounds.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135029"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475105","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 : 2026-01-15Epub Date: 2025-11-13DOI: 10.1016/j.tet.2025.135063
João Pedro de Albuquerque Souza , Giuliana Pavaneli , Sandra Radžiutė , Caroline Da Ros Montes D'Oca , Vincas Būda , Paulo Henrique Gorgatti Zarbin
The chemical ecology of crane flies (Diptera: Tipulidae) has only recently begun to be elucidated, creating a pressing need for enantiomerically pure standards to support structural identification and functional studies. In a previous investigation, the cuticular hydrocarbons (R)- and (S)-3-methylheneicosane were identified as male-specific components of Tipula autumnalis, with synthetic samples enabling both confirmation of their stereostructures and assessment of biological activity. Laboratory bioassays revealed that the (R)-enantiomer elicited an excitatory response in males, whereas the (S)-enantiomer acted as a repellent. In the present work, we detail the total enantiospecific synthesis of these compounds from methyl (S)-3-hydroxy-2-methylpropionate precursor. The route employs orthogonal protection, Wittig coupling with a C17 fragment, hydrogenation, and terminal one-carbon homologation, providing efficient access to long-chain methyl-branched hydrocarbons with full stereochemical control. This work establishes a robust and generalizable strategy for the synthesis of enantioenriched methyl-branched hydrocarbons and provides sufficient material to support all future chemical and behavioral studies in this species, paving the way for the development of targeted insect management strategies.
{"title":"Enantiospecific syntheses of (R)- and (S)-3-methylheneicosane, male-specific cuticular hydrocarbon of the crane fly Tipula autumnalis (Diptera: Tipulidae)","authors":"João Pedro de Albuquerque Souza , Giuliana Pavaneli , Sandra Radžiutė , Caroline Da Ros Montes D'Oca , Vincas Būda , Paulo Henrique Gorgatti Zarbin","doi":"10.1016/j.tet.2025.135063","DOIUrl":"10.1016/j.tet.2025.135063","url":null,"abstract":"<div><div>The chemical ecology of crane flies (Diptera: Tipulidae) has only recently begun to be elucidated, creating a pressing need for enantiomerically pure standards to support structural identification and functional studies. In a previous investigation, the cuticular hydrocarbons (<em>R</em>)- and (<em>S</em>)-3-methylheneicosane were identified as male-specific components of <em>Tipula autumnalis</em>, with synthetic samples enabling both confirmation of their stereostructures and assessment of biological activity. Laboratory bioassays revealed that the (<em>R</em>)-enantiomer elicited an excitatory response in males, whereas the (<em>S</em>)-enantiomer acted as a repellent. In the present work, we detail the total enantiospecific synthesis of these compounds from methyl (<em>S</em>)-3-hydroxy-2-methylpropionate precursor. The route employs orthogonal protection, Wittig coupling with a C17 fragment, hydrogenation, and terminal one-carbon homologation, providing efficient access to long-chain methyl-branched hydrocarbons with full stereochemical control. This work establishes a robust and generalizable strategy for the synthesis of enantioenriched methyl-branched hydrocarbons and provides sufficient material to support all future chemical and behavioral studies in this species, paving the way for the development of targeted insect management strategies.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135063"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145527168","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 : 2026-01-15Epub Date: 2025-10-26DOI: 10.1016/j.tet.2025.135023
Hanrong Liu, Junhui Jia
Mechanochromic luminescent (MCL) materials are a class of novel intelligent materials that exhibit reversible change in luminescence color and/or intensity upon external mechanical force stimulation, demonstrating significant application potential in fields of force sensors, anti-counterfeiting materials, optical storage, bioimaging, and inkless printing, etc. Over the past few decades, in sharp contrast to the traditional fluorescence quenching phenomenon, MCL materials with enhanced luminescence effects have attracted considerable attention due to their unique “off-on” or “turn-on” behavior, where the luminescence intensity or efficiency significantly increased under mechanical force. Focusing on this intriguing property, this review summarizes the latest advances in “turn-on” MCL organic luminophores, categorizing them based on structural features and associated luminescence mechanisms. It emphasizes the critical roles of intermolecular interactions and packing modes in regulating mechanochromic behavior and mechanical force-induced luminescence enhancement performance. Furthermore, this review prospects future development directions and challenges for mechanical force-induced chromic materials with luminescence enhancement, including the development of novel high-efficiency materials, exploration of practical application potential, and in-depth investigation of underlying luminescence mechanisms.
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