Vu H. Luu , Khoa H. D. Nguyen , Kien Q. Truong , Han B. Tran , Hoang V. M. Trinh , Thuy T. Ca , Tung T. Nguyen
A method is reported which allows for a three‐component cyclization of sulfoxonium ylides, aryl isothiocyanates, and amines to yield 2‐iminothiazolines. The method overcomes the limitation from the scope‐of‐substrate perspective. Success relies on the use of nickel(II) bromide, presumably acting as a Lewis acid catalyst. Investigation of substrate scopes reveals the compatibility of an array of useful functionalities.
{"title":"Nickel(II) Bromide Catalyzed Multicomponent Cyclization to Access 4‐Substituted 2‐Iminothiazolines","authors":"Vu H. Luu , Khoa H. D. Nguyen , Kien Q. Truong , Han B. Tran , Hoang V. M. Trinh , Thuy T. Ca , Tung T. Nguyen","doi":"10.1002/ejoc.202500830","DOIUrl":"10.1002/ejoc.202500830","url":null,"abstract":"<div><div>A method is reported which allows for a three‐component cyclization of sulfoxonium ylides, aryl isothiocyanates, and amines to yield 2‐iminothiazolines. The method overcomes the limitation from the scope‐of‐substrate perspective. Success relies on the use of nickel(II) bromide, presumably acting as a Lewis acid catalyst. Investigation of substrate scopes reveals the compatibility of an array of useful functionalities.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500830"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194971","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}
Amit Bijlwan , Priyanka Das , Prachi Bhatia , Vikas D. Ghule , Dheeraj Kumar
Herein, to fine‐tune the energetic properties of 2,4,6‐trinitrobenzene‐1,3‐diamine/diol, these are combined with tetrazole via a methylene bridge. This strategy unlocks the tunability of polynitroarenes performances via salt formation, which is restricted in directly CN connected polynitroarenes and azole derivatives. The amino/hydroxy functionalities between the nitro groups on the benzene ring provide extensive inter‐ and intramolecular hydrogen bonding interactions, contributing to improved stability, whereas the tetrazole ring increases the nitrogen percentage and energetic performance. Due to the presence of one and three labile protons in the amino derivative (compounds 4) and hydroxy derivative (compounds 5), respectively, a series of mono‐ and tricationic salts are prepared to further fine‐tune the overall performances. Among all the synthesized compounds, the tricationic energetic salt 10 (Dv = 8135 m s−1, IS > 40 J) exhibits energetic performance comparable to TATB and is insensitive. All the compounds are characterized through infrared spectroscopy, Nuclear Magnetic Resonance (NMR) spectroscopy, differential scanning calorimetry, elemental analysis, and high‐resolution mass spectra studies. The relationship between structure and properties is further explored using Hirshfeld surface, noncovalent interaction, Localized Orbital Locator (LOL)‐π, and electrostatic potential analysis.
{"title":"A Family of Methylene‐Bridged Fully Functionalized Polynitroarenes and Tetrazole‐Based Energetic Materials","authors":"Amit Bijlwan , Priyanka Das , Prachi Bhatia , Vikas D. Ghule , Dheeraj Kumar","doi":"10.1002/ejoc.202500823","DOIUrl":"10.1002/ejoc.202500823","url":null,"abstract":"<div><div>Herein, to fine‐tune the energetic properties of 2,4,6‐trinitrobenzene‐1,3‐diamine/diol, these are combined with tetrazole via a methylene bridge. This strategy unlocks the tunability of polynitroarenes performances via salt formation, which is restricted in directly CN connected polynitroarenes and azole derivatives. The amino/hydroxy functionalities between the nitro groups on the benzene ring provide extensive inter‐ and intramolecular hydrogen bonding interactions, contributing to improved stability, whereas the tetrazole ring increases the nitrogen percentage and energetic performance. Due to the presence of one and three labile protons in the amino derivative (compounds <strong>4</strong>) and hydroxy derivative (compounds <strong>5</strong>), respectively, a series of mono‐ and tricationic salts are prepared to further fine‐tune the overall performances. Among all the synthesized compounds, the tricationic energetic salt <strong>10</strong> (D<sub>v</sub> = 8135 m s<sup>−1</sup>, IS > 40 J) exhibits energetic performance comparable to TATB and is insensitive. All the compounds are characterized through infrared spectroscopy, Nuclear Magnetic Resonance (NMR) spectroscopy, differential scanning calorimetry, elemental analysis, and high‐resolution mass spectra studies. The relationship between structure and properties is further explored using Hirshfeld surface, noncovalent interaction, Localized Orbital Locator (LOL)‐π, and electrostatic potential analysis.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500823"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215988","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}
A Ni(OAc)2 catalyzed N‐formylation of primary sulfonamides using gaseous carbon dioxide is reported. A range of aromatic, heteroaromatic, and aliphatic sulfonamides are formylated under ambient pressure of carbon dioxide in a closed system. This redox‐neutral method represents a mechanistically novel and operationally convenient method for employing carbon dioxide as a formyl equivalent.
{"title":"Ni(OAc)2 Catalyzed N‐Formylation of Primary Sulfonamides Using Carbon Dioxide at Ambient Pressure","authors":"David Izuchukwu Ugwu , Ganesh Chandra Upreti , Ashish Garg , Anand Singh","doi":"10.1002/ejoc.202500369","DOIUrl":"10.1002/ejoc.202500369","url":null,"abstract":"<div><div>A Ni(OAc)<sub>2</sub> catalyzed <em>N</em>‐formylation of primary sulfonamides using gaseous carbon dioxide is reported. A range of aromatic, heteroaromatic, and aliphatic sulfonamides are formylated under ambient pressure of carbon dioxide in a closed system. This redox‐neutral method represents a mechanistically novel and operationally convenient method for employing carbon dioxide as a formyl equivalent.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500369"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296199","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}
Highly fluorinated biphenyls are valuable motifs in various applications. Traditional methods for their synthesis often require expensive catalysts, harsh conditions, and sensitive reagents. Herein, a practical, transition‐metal‐free strategy for the synthesis of highly fluorinated biphenyls is reported via nucleophilic aromatic substitution (S N Ar) between potassium perfluorobenzoates and polyfluoroarenes. This method through an operationally simple protocol, using bench‐stable nucleophiles, enabling efficient access to structurally diverse biphenyls. It offers broad substrate scope, good functional group tolerance, and operational simplicity, providing an alternative to existing methods.
高氟联苯在各种应用中都是有价值的基序。传统的合成方法通常需要昂贵的催化剂、苛刻的条件和敏感的试剂。本文报道了一种实用的、无过渡金属的高氟联苯合成策略，即在全氟苯甲酸钾和多氟芳烃之间通过亲核芳香取代（S N Ar）合成高氟联苯。该方法通过操作简单的协议，使用稳定的亲核试剂，能够有效地获得结构多样的联苯。它具有广泛的基板范围、良好的功能组容忍度和操作简单性，为现有方法提供了一种替代方案。
{"title":"Transition‐Metal‐Free Synthesis of Highly Fluorinated Biphenyls by Nucleophilic Aromatic Substitution (S N Ar) between Potassium Perfluorobenzoates and Polyfluoroarenes","authors":"Erjun Hao, Honghao Zhou, Xiangyang Liu, Ling Fang, Chun Zhang, Dandan Hu, Jun‐Qi Zhang, Hongjun Ren, Hai‐Ming Guo","doi":"10.1002/ejoc.202500966","DOIUrl":"https://doi.org/10.1002/ejoc.202500966","url":null,"abstract":"Highly fluorinated biphenyls are valuable motifs in various applications. Traditional methods for their synthesis often require expensive catalysts, harsh conditions, and sensitive reagents. Herein, a practical, transition‐metal‐free strategy for the synthesis of highly fluorinated biphenyls is reported via nucleophilic aromatic substitution (S <jats:sub>N</jats:sub> Ar) between potassium perfluorobenzoates and polyfluoroarenes. This method through an operationally simple protocol, using bench‐stable nucleophiles, enabling efficient access to structurally diverse biphenyls. It offers broad substrate scope, good functional group tolerance, and operational simplicity, providing an alternative to existing methods.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145611155","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}
Owing to the excellent biological activities of quinolines and organic chalcogenides, organosulfenylquinolines, which contain both sulfur and quinolinones, may have potential biological activity. To solve the existing problems for their generation, an electrochemical annulation/thiolation of o ‐vinylphenyl isocyanides with diorgano disulfides to give 2‐sulfenylquinolines is reported. As compared to previous methods, this procedure has the advantages of mild reaction conditions, good substrate applicability, and environmental friendliness.
{"title":"Electrochemical Annulation/Thiolation of o ‐Vinylphenyl Isocyanides with Diorgano Disulfides to Access 2‐Sulfenylquinolines","authors":"Jinyang Chen, Hongbiao Li, Qiao Ran, Zonglan Huang, Peifeng Ran, Yiwen Zhang, Yuejun Ouyang","doi":"10.1002/ejoc.202500962","DOIUrl":"https://doi.org/10.1002/ejoc.202500962","url":null,"abstract":"Owing to the excellent biological activities of quinolines and organic chalcogenides, organosulfenylquinolines, which contain both sulfur and quinolinones, may have potential biological activity. To solve the existing problems for their generation, an electrochemical annulation/thiolation of <jats:italic>o</jats:italic> ‐vinylphenyl isocyanides with diorgano disulfides to give 2‐sulfenylquinolines is reported. As compared to previous methods, this procedure has the advantages of mild reaction conditions, good substrate applicability, and environmental friendliness.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"36 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145611154","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}
A gold‐catalyzed reaction of 3‐aminopent‐4‐yn‐1‐ols is described. 2‐Arylidene‐3‐aminotetrahydrofurans are synthesized via intramolecular nucleophilic cyclization of the hydroxy group with the activated alkyne. When the reaction is carried out with phenols as an additional nucleophile and Sc(OTf)3 as an activating reagent, tetrahydrofuro[2,3‐b]benzofurans are obtained. The reaction proceeds via a deaminative nucleophilic substitution of 3‐aminopent‐4‐yn‐1‐ols with phenols, followed by a successive intramolecular cyclization of the two hydroxy groups with the activated alkyne. When 1,3‐dicarbonyl compounds are used as the nucleophile, the corresponding substituted tetrahydrofuro[2,3‐b]furans are formed. To further understand the nature of this reaction, the intramolecular nucleophilic addition of alkynyl diol intermediate with gold complex is investigated as a model substrate using DFT calculations.
{"title":"Synthesis of 3‐Aminotetrahydrofurans and Tetrahydrofuro[2,3‐b]furans by Gold‐Catalyzed Cyclization of 3‐Aminopent‐4‐yn‐1‐ols","authors":"Touya Kariya , Hiroto Yuraki , Masafumi Hayashi , Tsukasa Hirokane , Shinya Shiomi , Masahiro Yoshida","doi":"10.1002/ejoc.202500498","DOIUrl":"10.1002/ejoc.202500498","url":null,"abstract":"<div><div>A gold‐catalyzed reaction of 3‐aminopent‐4‐yn‐1‐ols is described. 2‐Arylidene‐3‐aminotetrahydrofurans are synthesized via intramolecular nucleophilic cyclization of the hydroxy group with the activated alkyne. When the reaction is carried out with phenols as an additional nucleophile and Sc(OTf)<sub>3</sub> as an activating reagent, tetrahydrofuro[2,3‐b]benzofurans are obtained. The reaction proceeds via a deaminative nucleophilic substitution of 3‐aminopent‐4‐yn‐1‐ols with phenols, followed by a successive intramolecular cyclization of the two hydroxy groups with the activated alkyne. When 1,3‐dicarbonyl compounds are used as the nucleophile, the corresponding substituted tetrahydrofuro[2,3‐b]furans are formed. To further understand the nature of this reaction, the intramolecular nucleophilic addition of alkynyl diol intermediate with gold complex is investigated as a model substrate using DFT calculations.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500498"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144500487","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}
Saravanan Gowrisankar , Marius Lang , Peter R. Schreiner
We report the synthesis and characterization of a new family of single‐component polyamides incorporating rigid diamantane monomers, and investigate their structural, thermal, and nonlinear optical properties. These polymers are largely amorphous and exhibit exceptional thermal stability, with decomposition events in the 400–600 °C range, significantly exceeding those of conventional nylons such as nylon‐6 and nylon‐66. Thermal analysis further shows that polyamides containing aromatic units retain higher residual yields than purely aliphatic analogues. Powder X‐Ray diffraction, dynamic light scattering, and scanning electron microscopy reveal pronounced morphological differences, ranging from irregular nanoscale particulates to smooth, rubbery domains. A direct correlation between morphology and optical behavior is observed: polyamides with disordered or finely particulate structures display intrinsic white‐light emission (WLE, 490–700 nm, λmax ≈ 610 nm) under continuous near‐infrared (980 nm) laser irradiation, whereas the smooth morphology suppresses this response. Importantly, this dopant‐free WLE is unprecedented for polyamides, identifying diamantane‐based polymers as an attractive platform for efficient, thermally robust, and cost‐effective organic light‐emitting materials.
{"title":"The Nonlinear Optical Behavior of Linear Diamantane Polyamides","authors":"Saravanan Gowrisankar , Marius Lang , Peter R. Schreiner","doi":"10.1002/ejoc.202500643","DOIUrl":"10.1002/ejoc.202500643","url":null,"abstract":"<div><div>We report the synthesis and characterization of a new family of single‐component polyamides incorporating rigid diamantane monomers, and investigate their structural, thermal, and nonlinear optical properties. These polymers are largely amorphous and exhibit exceptional thermal stability, with decomposition events in the 400–600 °C range, significantly exceeding those of conventional nylons such as nylon‐6 and nylon‐66. Thermal analysis further shows that polyamides containing aromatic units retain higher residual yields than purely aliphatic analogues. Powder X‐Ray diffraction, dynamic light scattering, and scanning electron microscopy reveal pronounced morphological differences, ranging from irregular nanoscale particulates to smooth, rubbery domains. A direct correlation between morphology and optical behavior is observed: polyamides with disordered or finely particulate structures display intrinsic white‐light emission (WLE, 490–700 nm, <em>λ</em><sub>max</sub> ≈ 610 nm) under continuous near‐infrared (980 nm) laser irradiation, whereas the smooth morphology suppresses this response. Importantly, this dopant‐free WLE is unprecedented for polyamides, identifying diamantane‐based polymers as an attractive platform for efficient, thermally robust, and cost‐effective organic light‐emitting materials.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500643"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215860","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}
Benzofuran derivatives are core components in many biologically active natural and synthetic compounds including approved drugs. Herein, an easy‐to‐access and TM‐free, one‐pot, three‐step synthesis of 2‐amino‐3‐aroyl‐5‐sulfonamide substituted benzo[b]furans bearing many functional groups of different electronic and steric nature using thioamides (as a 2C synthon) and N‐tosylbenzoquinone imine (as a CCO unit partner) at room temperature in open air is presented for the first time. The reaction proceeds via deprotonation/Michael addition/cyclization/aromatization cascades forming two new (CC and CO) bonds and one ring, liberating only H2S as a byproduct. High resolution mass spectrometry study endorses the key intermediates involved during reaction, validating excellent regio‐ and chemoselectivity. This protocol will not only provide an efficient and scalable method to access diverse benzo[b]furans that could be adaptable to late‐stage functionalization but also enrich the research domain of thioamides.
{"title":"Stitching β‐Ketothioamides with N‐Tosylbenzoquinone Imine: Transition‐Metal Free Site‐Selective Domino Synthesis of 2‐Amino‐3‐aroyl‐5‐sulfonamide Substituted Benzo[b]furans","authors":"Vimlesh Kumar Kanaujiya , Nimisha Gupta , Virendra Prasad , Maya Shankar Singh","doi":"10.1002/ejoc.202500675","DOIUrl":"10.1002/ejoc.202500675","url":null,"abstract":"<div><div>Benzofuran derivatives are core components in many biologically active natural and synthetic compounds including approved drugs. Herein, an easy‐to‐access and TM‐free, one‐pot, three‐step synthesis of 2‐amino‐3‐aroyl‐5‐sulfonamide substituted benzo[<em>b</em>]furans bearing many functional groups of different electronic and steric nature using thioamides (as a 2C synthon) and <em>N</em>‐tosylbenzoquinone imine (as a CCO unit partner) at room temperature in open air is presented for the first time. The reaction proceeds via deprotonation/Michael addition/cyclization/aromatization cascades forming two new (CC and CO) bonds and one ring, liberating only H<sub>2</sub>S as a byproduct. High resolution mass spectrometry study endorses the key intermediates involved during reaction, validating excellent regio‐ and chemoselectivity. This protocol will not only provide an efficient and scalable method to access diverse benzo[<em>b</em>]furans that could be adaptable to late‐stage functionalization but also enrich the research domain of thioamides.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500675"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183092","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}
The control of regio‐ and stereoselectivity in organic transformations remains a foundational challenge in synthetic chemistry. While chemoselectivity can often be influenced by careful selection of reagents or protective groups, controlling regio‐ and stereoselectivity is far more nuanced, often requiring highly specific reaction conditions. In this work, a unified approach for controlling both regio‐ and stereoselectivity across mechanistically related transformations is explored, specifically focusing on epoxide openings and carbonyl additions. It is demonstrated that the same environmental factors, here the nature of the Lewis acid (LA), can be leveraged to influence divergent outcomes in these two reaction types by amplifying inherent differences between reaction sites/faces, leading to highly selective transformations. The systematic evaluation of over 30 Lewis acids revealed a dichotomy between “labile” and “strong” activation modes, where strong LAs, such as AlCl3 and SnCl4, drive the highest levels of regio‐ and diastereoselectivity for both transformations. Further, there exists nuanced differences between the degree of influence of some LA within these mechanistically related transformations. These findings suggest that environmental factors can be broadly applied across different mechanistic classes to achieve selectivity, offering a versatile strategy for reaction optimization.
{"title":"Environmental Control of Regio‐/Stereoselectivity Across Mechanistically Similar Transformations","authors":"Anushka Asurumunige , Doris Itubo , Kerry Gilmore","doi":"10.1002/ejoc.202500299","DOIUrl":"10.1002/ejoc.202500299","url":null,"abstract":"<div><div>The control of regio‐ and stereoselectivity in organic transformations remains a foundational challenge in synthetic chemistry. While chemoselectivity can often be influenced by careful selection of reagents or protective groups, controlling regio‐ and stereoselectivity is far more nuanced, often requiring highly specific reaction conditions. In this work, a unified approach for controlling both regio‐ and stereoselectivity across mechanistically related transformations is explored, specifically focusing on epoxide openings and carbonyl additions. It is demonstrated that the same environmental factors, here the nature of the Lewis acid (LA), can be leveraged to influence divergent outcomes in these two reaction types by amplifying inherent differences between reaction sites/faces, leading to highly selective transformations. The systematic evaluation of over 30 Lewis acids revealed a dichotomy between “labile” and “strong” activation modes, where strong LAs, such as AlCl<sub>3</sub> and SnCl<sub>4</sub>, drive the highest levels of regio‐ and diastereoselectivity for both transformations. Further, there exists nuanced differences between the degree of influence of some LA within these mechanistically related transformations. These findings suggest that environmental factors can be broadly applied across different mechanistic classes to achieve selectivity, offering a versatile strategy for reaction optimization.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500299"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153589","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}
Niklas Geue , Kim Greis , Sabrina Omoregbee‐Leichnitz , Carla Kirschbaum , Chun‐Wei Chang , Gerard Meijer , Gert von Helden , Peter H. Seeberger , Kevin Pagel
The stereoselective synthesis of 1,2‐cis glycosidic bonds is historically challenging, and a common synthetic approach is based on the participation of remote protecting ester groups. Common intermediates of glycosylation reactions are glycosyl cations, whose structures are difficult to characterize. Here, the glycosylation reactions and structure of the glycosyl cations of galactose and mannose are investigated when protected with levulinic acid (Lev) at C4 and/or C6, respectively. The glycosyl cations can be assigned to rearranged structures as a consequence of ring opening, as well as dioxolenium ions that suggest remote participation. Some evidence for the long‐range interaction of the Lev keto group is found as previously proposed, which could explain unusual solution‐phase stereoselectivities observed.
{"title":"Influence of Levulinoyl Protecting Groups on Glycosylation Stereoselectivity and Glycosyl Cation Structure","authors":"Niklas Geue , Kim Greis , Sabrina Omoregbee‐Leichnitz , Carla Kirschbaum , Chun‐Wei Chang , Gerard Meijer , Gert von Helden , Peter H. Seeberger , Kevin Pagel","doi":"10.1002/ejoc.202500732","DOIUrl":"10.1002/ejoc.202500732","url":null,"abstract":"<div><div>The stereoselective synthesis of 1,2‐<em>cis</em> glycosidic bonds is historically challenging, and a common synthetic approach is based on the participation of remote protecting ester groups. Common intermediates of glycosylation reactions are glycosyl cations, whose structures are difficult to characterize. Here, the glycosylation reactions and structure of the glycosyl cations of galactose and mannose are investigated when protected with levulinic acid (Lev) at C4 and/or C6, respectively. The glycosyl cations can be assigned to rearranged structures as a consequence of ring opening, as well as dioxolenium ions that suggest remote participation. Some evidence for the long‐range interaction of the Lev keto group is found as previously proposed, which could explain unusual solution‐phase stereoselectivities observed.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500732"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134513","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}
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