Serhii Yu. Lukyanenko, Danylo A. Nosyk, Dmytro S. Granat, Andrii V. Kozytskyi, Oleksandr O. Yurchenko, Oleksandr Pokholenko, Alexey V. Dobrydnev, Oleksandr O. Grygorenko
A reliable methodology for the multigram preparation of diastereomerically enriched 3,6‐disubstituted bicyclo[3.2.0]heptane building blocks is proposed. The strategy is based on [2 + 2] cycloaddition of 3‐substituted cyclopentene derivatives and dichloroketene, followed by a diastereoselective reduction reaction. Despite both steps lacking stereospecificity, the target bicyclic racemic building blocks (including amino acids and amino alcohols) could be obtained as pure diastereomers on up to a 34.4 g scale. Structural characterization of the title scaffolds using exit vector plot formalism showed their potential for cycloalkane/benzene isosteric replacements in medicinal chemistry.
{"title":"Synthesis and Structural Characterization of 3,6‐Disubstituted Bicyclo[3.2.0]heptane Building Blocks: Promising Saturated Bicyclic Isosteres of Cycloalkanes/Benzene","authors":"Serhii Yu. Lukyanenko, Danylo A. Nosyk, Dmytro S. Granat, Andrii V. Kozytskyi, Oleksandr O. Yurchenko, Oleksandr Pokholenko, Alexey V. Dobrydnev, Oleksandr O. Grygorenko","doi":"10.1002/ejoc.70334","DOIUrl":"https://doi.org/10.1002/ejoc.70334","url":null,"abstract":"A reliable methodology for the multigram preparation of diastereomerically enriched 3,6‐disubstituted bicyclo[3.2.0]heptane building blocks is proposed. The strategy is based on [2 + 2] cycloaddition of 3‐substituted cyclopentene derivatives and dichloroketene, followed by a diastereoselective reduction reaction. Despite both steps lacking stereospecificity, the target bicyclic racemic building blocks (including amino acids and amino alcohols) could be obtained as pure diastereomers on up to a 34.4 g scale. Structural characterization of the title scaffolds using exit vector plot formalism showed their potential for cycloalkane/benzene isosteric replacements in medicinal chemistry.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"91 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146778767","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 selective modification of aromatic ring systems through single‐atom skeletal editing has emerged as a transformative strategy in modern organic synthesis. Among the most compelling advances are carbon‐to‐nitrogen (C‐to‐N) and nitrogen‐to‐carbon (N‐to‐C) transmutations, which enable precise atomic substitutions within heteroaromatic frameworks without disrupting the surrounding molecular architecture. This review comprehensively summarizes recent developments in these two complementary transformations, highlighting both mechanistic innovations and synthetic applications. C‐to‐N transmutation strategies, including oxidative ring expansion and electrophilic rearrangement, have enabled the conversion of quinolines and related azaarenes into pharmaceutically relevant quinazolines. Conversely, N‐to‐C editing approaches such as ring‐opening, skeletal rearrangement, and rearomatization allow the deconstruction of nitrogen‐containing heterocycles like pyridines into substituted benzenes. These methodologies have opened new avenues in drug design, late‐stage functionalization, and heterocycle diversification. The review also discusses the current limitations, mechanistic insights, and future opportunities for extending single atom editing to broader classes of aromatic systems, positioning this field at the forefront of molecular editing and precision synthesis.
{"title":"Single‐Atom Skeletal Editing of Aromatics: Advances in Carbon‐to‐Nitrogen and Nitrogen‐to‐Carbon Transmutation","authors":"Ankit Kachore , Varun Aggarwal , Ekta Bala , Hemant Singh , Manickam Selvaraj , Mohammed A. Assiri , Saima , Rakesh Kumar , Praveen Kumar Verma","doi":"10.1002/ejoc.202501188","DOIUrl":"10.1002/ejoc.202501188","url":null,"abstract":"<div><div>The selective modification of aromatic ring systems through single‐atom skeletal editing has emerged as a transformative strategy in modern organic synthesis. Among the most compelling advances are carbon‐to‐nitrogen (C‐to‐N) and nitrogen‐to‐carbon (N‐to‐C) transmutations, which enable precise atomic substitutions within heteroaromatic frameworks without disrupting the surrounding molecular architecture. This review comprehensively summarizes recent developments in these two complementary transformations, highlighting both mechanistic innovations and synthetic applications. C‐to‐N transmutation strategies, including oxidative ring expansion and electrophilic rearrangement, have enabled the conversion of quinolines and related azaarenes into pharmaceutically relevant quinazolines. Conversely, N‐to‐C editing approaches such as ring‐opening, skeletal rearrangement, and rearomatization allow the deconstruction of nitrogen‐containing heterocycles like pyridines into substituted benzenes. These methodologies have opened new avenues in drug design, late‐stage functionalization, and heterocycle diversification. The review also discusses the current limitations, mechanistic insights, and future opportunities for extending single atom editing to broader classes of aromatic systems, positioning this field at the forefront of molecular editing and precision synthesis.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202501188"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005793","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 : 2026-02-23Epub Date: 2026-02-05DOI: 10.1002/ejoc.202500937
Guy Pillon , Carlyle Mackenzie , Daniel Zell , Lauren E. Sirois
Photocatalytic reductive radical‐polar crossover is a versatile platform for achieving carbon–carbon bond formations under mild conditions and is complementary to traditional radical reactivity. Herein, we report a study on the reactivity of esters and ketones under this platform to produce cyclic ketone and alcohol products, respectively. The process is amenable to a variety of functionalized systems, and mechanistic experiments suggest intermediacy of both a benzylic radical and anion arising from photocatalytic reduction.
{"title":"Cyclization of Carbonyl Electrophiles via Dual HAT/Photoredox‐Catalyzed Reductive Radical‐Polar Crossover","authors":"Guy Pillon , Carlyle Mackenzie , Daniel Zell , Lauren E. Sirois","doi":"10.1002/ejoc.202500937","DOIUrl":"10.1002/ejoc.202500937","url":null,"abstract":"<div><div>Photocatalytic reductive radical‐polar crossover is a versatile platform for achieving carbon–carbon bond formations under mild conditions and is complementary to traditional radical reactivity. Herein, we report a study on the reactivity of esters and ketones under this platform to produce cyclic ketone and alcohol products, respectively. The process is amenable to a variety of functionalized systems, and mechanistic experiments suggest intermediacy of both a benzylic radical and anion arising from photocatalytic reduction.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202500937"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014607","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 : 2026-02-23Epub Date: 2026-02-05DOI: 10.1002/ejoc.202500981
Jinhua Wang , Tiantian Shao , Ruiling Huang , Ruhai Zuo , Qiaoling Zhang , Chengfeng Xiong , Zhiping Le
Molecular confinement is a viable method to fine‐tune the reactivity of chemical species. Metal–organic cages, which have large void spaces within, are especially attractive entities for encapsulating various guests. Here, a water‐soluble flexible metal–organic cage was used to confine two guest molecules, as either homo‐ or heterodimers with a high uptake efficiency. Photo irradiation of the inclusion complexes results in a smooth photo [2 + 2] dimerization reaction in aqueous solution despite the flexibility of this metal–organic cage. The preorganization of two molecules within the cage was responsible for the smooth photo‐dimerization, both for the homodimer and heterodimer. Kinetic study of the photoreaction revealed a pseudo‐first‐order reaction, implying a preformed dimer of guests within the cage was responsible for the reaction.
{"title":"Confinement‐Induced [2 + 2] Photodimerization of Vinylenes Within a Flexible Metal–Organic Cage","authors":"Jinhua Wang , Tiantian Shao , Ruiling Huang , Ruhai Zuo , Qiaoling Zhang , Chengfeng Xiong , Zhiping Le","doi":"10.1002/ejoc.202500981","DOIUrl":"10.1002/ejoc.202500981","url":null,"abstract":"<div><div>Molecular confinement is a viable method to fine‐tune the reactivity of chemical species. Metal–organic cages, which have large void spaces within, are especially attractive entities for encapsulating various guests. Here, a water‐soluble flexible metal–organic cage was used to confine two guest molecules, as either homo‐ or heterodimers with a high uptake efficiency. Photo irradiation of the inclusion complexes results in a smooth photo [2 + 2] dimerization reaction in aqueous solution despite the flexibility of this metal–organic cage. The preorganization of two molecules within the cage was responsible for the smooth photo‐dimerization, both for the homodimer and heterodimer. Kinetic study of the photoreaction revealed a pseudo‐first‐order reaction, implying a preformed dimer of guests within the cage was responsible for the reaction.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202500981"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043145","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 metal‐free annulative coupling strategy has been developed to synthesize functionalized thiazolidine‐4‐ones from β‐ketothioamides and α‐ester sulfoxonium ylides. This cascade process proceeds via concurrent CS and CN bond formation under mild conditions, delivering a wide range of thiazolidine‐4‐one derivatives in good‐to‐high yields. The method exhibits excellent functional group tolerance, broad substrate scope, and operational simplicity, with most products isolated via filtration without chromatography. The scalability and synthetic utility were demonstrated through gram‐scale synthesis and oxidative late‐stage functionalization, highlighting the potential of this strategy for accessing structurally diverse heterocycles.
{"title":"Annulative Coupling of β‐Ketothioamides with α‐Ester Sulfoxonium Ylides: A Practical Route to Functionalized Thiazolidine‐4‐Ones","authors":"Trayambek Nath Chaubey , Ajay Kant Gola , Rahul Kumar Saini , Satyendra Kumar Pandey","doi":"10.1002/ejoc.202501166","DOIUrl":"10.1002/ejoc.202501166","url":null,"abstract":"<div><div>A metal‐free annulative coupling strategy has been developed to synthesize functionalized thiazolidine‐4‐ones from β‐ketothioamides and α‐ester sulfoxonium ylides. This cascade process proceeds via concurrent CS and CN bond formation under mild conditions, delivering a wide range of thiazolidine‐4‐one derivatives in good‐to‐high yields. The method exhibits excellent functional group tolerance, broad substrate scope, and operational simplicity, with most products isolated via filtration without chromatography. The scalability and synthetic utility were demonstrated through gram‐scale synthesis and oxidative late‐stage functionalization, highlighting the potential of this strategy for accessing structurally diverse heterocycles.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202501166"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005791","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 simple and atom‐economical protocol to access racemic and nonracemic γ,γ‐diaryl/heteroaryl‐substituted propylamines in excellent yields (up to 98%) and with moderate enantiomeric excess (up to 62%) starting from azetidines and electron rich arenes/heteroarenes is described. The reaction involves Magic Blue‐initiated and incipient SbCl5‐catalyzed SN2‐type nucleophilic ring‐opening of activated azetidines with electron rich arenes/heteroarene under mild reaction conditions. The methodology has been efficiently used for the formal synthesis of optically active Tolterodine, an antimuscarinic drug.
{"title":"Magic Blue Initiated SN2–Type Ring Opening of Azetidines with Electron‐Rich Arenes/Heteroarenes: Formal Synthesis of Nonracemic Tolterodine","authors":"Shishir Singh , Bharat Singh , Suraj Kashyap , Manas K. Ghorai","doi":"10.1002/ejoc.202500836","DOIUrl":"10.1002/ejoc.202500836","url":null,"abstract":"<div><div>A simple and atom‐economical protocol to access racemic and nonracemic <em>γ</em>,<em>γ</em>‐diaryl/heteroaryl‐substituted propylamines in excellent yields (up to 98%) and with moderate enantiomeric excess (up to 62%) starting from azetidines and electron rich arenes/heteroarenes is described. The reaction involves Magic Blue‐initiated and incipient SbCl<sub>5</sub>‐catalyzed S<sub>N</sub>2‐type nucleophilic ring‐opening of activated azetidines with electron rich arenes/heteroarene under mild reaction conditions. The methodology has been efficiently used for the formal synthesis of optically active Tolterodine, an antimuscarinic drug.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202500836"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043143","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 : 2026-02-23Epub Date: 2026-02-05DOI: 10.1002/ejoc.202501126
Yu‐Hang Mi , Zhi‐Yu Wang , Ya‐Hui Wang , Kuo Wang , Yue Zhang , Ya‐Qi Yang , Xian‐Yi Huang , Shun‐Xin Zhang , Hong‐Wu Zhao
Under the catalysis of Pd2(dba)3 (10 mol%) and phosphoramidite (±)‐L13 (20 mol%) in 1,2‐DCE at 80°C, the three‐component cascade cyclization of nitrones, arylsulfonyl azides, and isocyanides proceeded readily and delivered 5‐imino‐1,2,4‐oxadiazolidines in reasonable chemical yields. The chemical structure of one title compound has been confirmed by X‐ray diffraction analysis, and the others are suggested by inference.
{"title":"Three‐Component Cascade Cyclization of Nitrones, Arylsulfonyl Azides, and Isocyanides for Synthesis of 5‐Imino‐1,2,4‐Oxadiazolidines","authors":"Yu‐Hang Mi , Zhi‐Yu Wang , Ya‐Hui Wang , Kuo Wang , Yue Zhang , Ya‐Qi Yang , Xian‐Yi Huang , Shun‐Xin Zhang , Hong‐Wu Zhao","doi":"10.1002/ejoc.202501126","DOIUrl":"10.1002/ejoc.202501126","url":null,"abstract":"<div><div>Under the catalysis of Pd<sub>2</sub>(dba)<sub>3</sub> (10 mol%) and phosphoramidite (±)‐<strong>L13</strong> (20 mol%) in 1,2‐DCE at 80°C, the three‐component cascade cyclization of nitrones, arylsulfonyl azides, and isocyanides proceeded readily and delivered 5‐imino‐1,2,4‐oxadiazolidines in reasonable chemical yields. The chemical structure of one title compound has been confirmed by X‐ray diffraction analysis, and the others are suggested by inference.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202501126"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993351","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 : 2026-02-23Epub Date: 2026-02-05DOI: 10.1002/ejoc.202501209
Eurípedes de Aguiar , Mônica F. Z. J. Toledo , Flávia Manarin , João H. de Araujo‐Neto , Milene M. Hornink , Hélio A. Stefani
Suzuki–Miyaura coupling has been widely explored, particularly in the development of pharmaceutically relevant structures. Its carbonylative variant enables the insertion of a CO bridge, granting access to a variety of bioactive biaryl ketone scaffolds. Herein, we describe a carbonylative Suzuki–Miyaura strategy for the preparation of a series of C‐acyl glycosides, thereby expanding the chemical space for the development of new derivatives in glycochemistry. The reaction proceeds under Pyridine‐Enhanced Precatalyst Preparation, Stabilization, and Initiation (PEPPSI‐IPr) ([1,3‐Bis(2,6‐Diisopropylphenyl)imidazol‐2‐ylidene](3‐chloropyridyl)palladium(II) dichloride) catalysis, employing Mo(CO)6 as a solid CO source for the in situ generation of CO, which enables the selective formation of the carbonylated products. The desired compounds were obtained in synthetically useful yields (up to 84%).
{"title":"Carbonylative Suzuki–Miyaura Coupling of 1‐Iodoglycals Mediated by the N‐Heterocyclic Carbene Catalyst PEPPSI: Preparation of C‐Acyl Glycosides","authors":"Eurípedes de Aguiar , Mônica F. Z. J. Toledo , Flávia Manarin , João H. de Araujo‐Neto , Milene M. Hornink , Hélio A. Stefani","doi":"10.1002/ejoc.202501209","DOIUrl":"10.1002/ejoc.202501209","url":null,"abstract":"<div><div>Suzuki–Miyaura coupling has been widely explored, particularly in the development of pharmaceutically relevant structures. Its carbonylative variant enables the insertion of a CO bridge, granting access to a variety of bioactive biaryl ketone scaffolds. Herein, we describe a carbonylative Suzuki–Miyaura strategy for the preparation of a series of <em>C</em>‐acyl glycosides, thereby expanding the chemical space for the development of new derivatives in glycochemistry. The reaction proceeds under Pyridine‐Enhanced Precatalyst Preparation, Stabilization, and Initiation (PEPPSI‐IPr) ([1,3‐Bis(2,6‐Diisopropylphenyl)imidazol‐2‐ylidene](3‐chloropyridyl)palladium(II) dichloride) catalysis, employing Mo(CO)<sub>6</sub> as a solid CO source for the in situ generation of CO, which enables the selective formation of the carbonylated products. The desired compounds were obtained in synthetically useful yields (up to 84%).</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202501209"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993363","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 : 2026-02-23Epub Date: 2026-02-05DOI: 10.1002/ejoc.202500991
Jiang‐Yu Li , Yu‐Fei Yao , Meng‐Zhu Xu , Wen‐Jin Xu , Cheng‐Pan Zhang
2,2,2‐trifluoroethyl sulfonium salts have emerged as the highly versatile trifluoroalkyl reagents in modern organic synthesis, due to their exceptional stability, ready availability, and ease of handling. 2,2,2‐Trifluoroethyl diphenylsulfonium salt has enabled many innovative trifluoroalkylation strategies, including photoredox trifluoroethylations, Fe‐catalyzed insertions, cyclopropanations, Johnson–Corey–Chaykovsky reactions, and [4 + 1] annulations, for the concise synthesis of a great deal of trifluoroethylated compounds and a variety of trifluoromethylated cyclopropanes, epoxides, aziridines, pyrrole derivatives, and pyrazolines, respectively, with high diastereoselectivity. This salt has also been used as an efficient cross‐coupling partner in the Pd‐ or Pd/Cu‐catalyzed Mizoroki–Heck, Suzuki–Miyaura, and Sonogashira arylation reactions. 2,2,2‐Trifluoroethyl sulfonium analogues, including pentafluoroethyl, α‐diazo trifluoroethyl, and 1‐(trifluoromethyl)cyclopropyl sulfonium salts, have been developed to meet a wider range of synthetic requirements. These reagents can readily introduce pentafluoroethyl group, serve as an equivalent of trifluoromethyl carbyne cation, allow the simultaneous transfer of both trifluoromethyl and diazo groups, and enable the direct radical trifluoromethylcyclopropylation, highlighting their significant potentials for synthetic applications in pharmaceuticals, agrochemicals, and functional materials. This review provides a comprehensive summary of 2,2,2‐trifluoroethyl diphenylsulfonium salt and its analogues in organic synthesis, with emphasis on trifluoroalkylation and annulation.
{"title":"An Overview of 2,2,2‐Trifluoroethyl Sulfonium Salts: Preparation and Synthetic Applications","authors":"Jiang‐Yu Li , Yu‐Fei Yao , Meng‐Zhu Xu , Wen‐Jin Xu , Cheng‐Pan Zhang","doi":"10.1002/ejoc.202500991","DOIUrl":"10.1002/ejoc.202500991","url":null,"abstract":"<div><div>2,2,2‐trifluoroethyl sulfonium salts have emerged as the highly versatile trifluoroalkyl reagents in modern organic synthesis, due to their exceptional stability, ready availability, and ease of handling. 2,2,2‐Trifluoroethyl diphenylsulfonium salt has enabled many innovative trifluoroalkylation strategies, including photoredox trifluoroethylations, Fe‐catalyzed insertions, cyclopropanations, Johnson–Corey–Chaykovsky reactions, and [4 + 1] annulations, for the concise synthesis of a great deal of trifluoroethylated compounds and a variety of trifluoromethylated cyclopropanes, epoxides, aziridines, pyrrole derivatives, and pyrazolines, respectively, with high diastereoselectivity. This salt has also been used as an efficient cross‐coupling partner in the Pd‐ or Pd/Cu‐catalyzed Mizoroki–Heck, Suzuki–Miyaura, and Sonogashira arylation reactions. 2,2,2‐Trifluoroethyl sulfonium analogues, including pentafluoroethyl, <em>α</em>‐diazo trifluoroethyl, and 1‐(trifluoromethyl)cyclopropyl sulfonium salts, have been developed to meet a wider range of synthetic requirements. These reagents can readily introduce pentafluoroethyl group, serve as an equivalent of trifluoromethyl carbyne cation, allow the simultaneous transfer of both trifluoromethyl and diazo groups, and enable the direct radical trifluoromethylcyclopropylation, highlighting their significant potentials for synthetic applications in pharmaceuticals, agrochemicals, and functional materials. This review provides a comprehensive summary of 2,2,2‐trifluoroethyl diphenylsulfonium salt and its analogues in organic synthesis, with emphasis on trifluoroalkylation and annulation.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202500991"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005792","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 : 2026-02-23Epub Date: 2026-02-05DOI: 10.1002/ejoc.202501026
Xiaoqiong Fu , Ying Wang , Huan Li , Fangni Hu , Huaiyu Huang , Xuyang Gong , Wenbo Xu , Shuangshuang Zhang , Haifeng Wang , Shuangxi Gu
An efficient approach for the ring‐opening of benzoxazole derivatives involves utilizing diazo compounds in the presence of Fe(OTf)3 as a catalyst. This method enables the efficient conversion of the oxazole ring into highly functionalized products that bear N‐amino, amide, and hydroxy groups. This approach overcomes the strong steric hindrance of benzoxazole when it carries substituents at the C2 position. And it has the advantages of high yield, broad substrate scope, efficient atom utilization, and so on. Moreover, some of these compounds exhibit antibacterial activity, which offer a valuable reference for the future development of novel antimicrobial agents.
{"title":"Ring‐Opening Reaction of Benzoxazole Derivatives with Diazo Compounds Catalyzed by Fe(OTf)3","authors":"Xiaoqiong Fu , Ying Wang , Huan Li , Fangni Hu , Huaiyu Huang , Xuyang Gong , Wenbo Xu , Shuangshuang Zhang , Haifeng Wang , Shuangxi Gu","doi":"10.1002/ejoc.202501026","DOIUrl":"10.1002/ejoc.202501026","url":null,"abstract":"<div><div>An efficient approach for the ring‐opening of benzoxazole derivatives involves utilizing diazo compounds in the presence of Fe(OTf)<sub>3</sub> as a catalyst. This method enables the efficient conversion of the oxazole ring into highly functionalized products that bear <em>N</em>‐amino, amide, and hydroxy groups. This approach overcomes the strong steric hindrance of benzoxazole when it carries substituents at the C2 position. And it has the advantages of high yield, broad substrate scope, efficient atom utilization, and so on. Moreover, some of these compounds exhibit antibacterial activity, which offer a valuable reference for the future development of novel antimicrobial agents.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 7","pages":"Article e202501026"},"PeriodicalIF":2.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005837","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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