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}
Stamatis K. Serviou , Petros L. Gkizis , Darío Puchán Sánchez , Soussana Azar , Arthur H. G. David , Clement Cabanetos , Christoforos G. Kokotos
Herein, a sustainable and eco‐friendly protocol is reported for the aerobic photochemical oxidation of boronic acids or esters, utilizing a dibenzothioxanthene imide as the photocatalyst at a very low catalyst loading (0.01%) in 2‐propanol, employing a 456 nm irradiation source. Additionally, this protocol is successfully applied to a variety of substrates.
{"title":"Visible Light‐Promoted Aerobic Oxidation of Boronic Acids and Esters Utilizing a Benzothioxanthene Imide as the Photocatalyst","authors":"Stamatis K. Serviou , Petros L. Gkizis , Darío Puchán Sánchez , Soussana Azar , Arthur H. G. David , Clement Cabanetos , Christoforos G. Kokotos","doi":"10.1002/ejoc.202500782","DOIUrl":"10.1002/ejoc.202500782","url":null,"abstract":"<div><div>Herein, a sustainable and eco‐friendly protocol is reported for the aerobic photochemical oxidation of boronic acids or esters, utilizing a dibenzothioxanthene imide as the photocatalyst at a very low catalyst loading (0.01%) in 2‐propanol, employing a 456 nm irradiation source. Additionally, this protocol is successfully applied to a variety of substrates.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500782"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154084","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 , Steffen Schröder , Neeshma Mathew , Jörn Schmedt auf der Günne , Peter R. Schreiner
We report a series of diamantane polyesters synthesized as head‐to‐head and side‐to‐side linear chain polymers. The incorporation of the bulky and rigid diamantyl moiety significantly enhances the thermal stabilities of these polymers compared to well‐established linear aliphatic polyesters, such as poly(ε‐caprolactone), poly(lactic acid), poly(butylene succinate), and poly(glycolic acid). This enhancement is confirmed by thermogravimetric analyzes, which show degradation onsets in the range of 520 to 580 °C. The structural characterization of these polyesters posed significant challenges due to virtual insolubility in organic solvents, limiting the use of techniques such as mass spectrometry and liquid‐state nuclear magnetic resonance (NMR) spectroscopy. To address these challenges, a genetic algorithm for structure prediction based on periodic density functional theory computations was employed, yielding a structure that closely matches the powder X‐ray diffraction data. Heavily constrained Rietveld refinement provided excellent agreement with the experimental results. These findings, combined with solid‐state NMR data, have been integrated to provide a comprehensive understanding of the polyester properties. These polyesters demonstrate promising nonlinear optical responses, including white‐light emission upon continuous infrared laser irradiation, making them candidates for optoelectronic applications.
{"title":"A Density Functional Theory‐Genetic Algorithm Approach for the Structural Elucidation of Linear Diamantane Polyesters and their Nonlinear Optical Properties","authors":"Saravanan Gowrisankar , Marius Lang , Steffen Schröder , Neeshma Mathew , Jörn Schmedt auf der Günne , Peter R. Schreiner","doi":"10.1002/ejoc.202500645","DOIUrl":"10.1002/ejoc.202500645","url":null,"abstract":"<div><div>We report a series of diamantane polyesters synthesized as head‐to‐head and side‐to‐side linear chain polymers. The incorporation of the bulky and rigid diamantyl moiety significantly enhances the thermal stabilities of these polymers compared to well‐established linear aliphatic polyesters, such as poly(ε‐caprolactone), poly(lactic acid), poly(butylene succinate), and poly(glycolic acid). This enhancement is confirmed by thermogravimetric analyzes, which show degradation onsets in the range of 520 to 580 °C. The structural characterization of these polyesters posed significant challenges due to virtual insolubility in organic solvents, limiting the use of techniques such as mass spectrometry and liquid‐state nuclear magnetic resonance (NMR) spectroscopy. To address these challenges, a genetic algorithm for structure prediction based on periodic density functional theory computations was employed, yielding a structure that closely matches the powder X‐ray diffraction data. Heavily constrained Rietveld refinement provided excellent agreement with the experimental results. These findings, combined with solid‐state NMR data, have been integrated to provide a comprehensive understanding of the polyester properties. These polyesters demonstrate promising nonlinear optical responses, including white‐light emission upon continuous infrared laser irradiation, making them candidates for optoelectronic applications.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500645"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235390","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}
Virgil Percec , Jasper Adamson , Devendra S. Maurya
This concept article discusses recent developments in activated esters, including fluorinated activated esters and other activated carboxylic acid derivatives. Activated carboxylic acid derivatives, including esters, are of interest since 1901 when Emil Fischer prepared the first peptide, and soon after, for the synthesis of Nylons, Kevlar, and other condensation polymers. Since the synthesis of sequence‐defined peptides and methodologies for their construction relied mostly on the development of activated ester derivatives, the preparation of the peptide and amide bond is used as a strategy for the organization and the development of this concept article. Therefore, the acyl chlorides, anhydrides, numerous nonfluorinated activated esters, and fluorinated activated esters, including pentachlorophenyl, pentafluorophenyl, hexafluoroisopropyl, and other fluorinated esters, will be discussed in aminolysis and transesterification reactions. The synthesis of peptide and amide bond, the modification of polymers, the bioorthogonal chemistry, and the living chain‐growth condensation polymerization are also briefly discussed. This concept article ends with a brief mention of the resurgence of acyl fluoride in organic and macromolecular chemistry.
{"title":"Activation in Organic and Macromolecular Including Peptide Synthesis by Fluorinated Carboxylic Acids and Derivatives","authors":"Virgil Percec , Jasper Adamson , Devendra S. Maurya","doi":"10.1002/ejoc.202500776","DOIUrl":"10.1002/ejoc.202500776","url":null,"abstract":"<div><div>This concept article discusses recent developments in activated esters, including fluorinated activated esters and other activated carboxylic acid derivatives. Activated carboxylic acid derivatives, including esters, are of interest since 1901 when Emil Fischer prepared the first peptide, and soon after, for the synthesis of Nylons, Kevlar, and other condensation polymers. Since the synthesis of sequence‐defined peptides and methodologies for their construction relied mostly on the development of activated ester derivatives, the preparation of the peptide and amide bond is used as a strategy for the organization and the development of this concept article. Therefore, the acyl chlorides, anhydrides, numerous nonfluorinated activated esters, and fluorinated activated esters, including pentachlorophenyl, pentafluorophenyl, hexafluoroisopropyl, and other fluorinated esters, will be discussed in aminolysis and transesterification reactions. The synthesis of peptide and amide bond, the modification of polymers, the bioorthogonal chemistry, and the living chain‐growth condensation polymerization are also briefly discussed. This concept article ends with a brief mention of the resurgence of acyl fluoride in organic and macromolecular chemistry.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 44","pages":"Article e202500776"},"PeriodicalIF":2.7,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183093","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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