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":"https://doi.org/10.1002/ejoc.202500991","url":null,"abstract":"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, <i>α</i>-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.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-21","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}
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":"https://doi.org/10.1002/ejoc.202501026","url":null,"abstract":"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 <i>N</i>-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.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"64 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-21","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}
Ankit Kachore, Varun Aggarwal, Ekta Bala, Hemant Singh, Manickam Selvaraj, Mohammed A. Assiri, Saima, Rakesh Kumar, Praveen Kumar Verma
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":"https://doi.org/10.1002/ejoc.202501188","url":null,"abstract":"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.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"39 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-20","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}
Ami Sakurai, Shuya Yamaguchi, Yasunao Hattori, Atsushi Kawamura, Hidefumi Makabe
The Front Cover depicts the tropical region where the plant Annona squamosa, the source of mucocin (an acetogenin), grows. It also includes the fruit of this plant. To represent the convergent synthesis in this study, three fragments are shown flowing from three rivers, converging in a lake where mucocin is formed. Furthermore, oxypalladation is depicted as a precursor passing through a tunnel. The coordination of palladium to the olefinic portion is illustrated by an Amazon river dolphin. More information can be found in the Research Article by H. Makabe and co-workers (DOI: 10.1002/ejoc.202500990).
{"title":"Front Cover: Synthesis of (−)-Mucocin Using a Diastereoselective Oxypalladation and Cross-Metathesis (Eur. J. Org. Chem. 2/2026)","authors":"Ami Sakurai, Shuya Yamaguchi, Yasunao Hattori, Atsushi Kawamura, Hidefumi Makabe","doi":"10.1002/ejoc.70313","DOIUrl":"10.1002/ejoc.70313","url":null,"abstract":"<p><b>The Front Cover</b> depicts the tropical region where the plant Annona squamosa, the source of mucocin (an acetogenin), grows. It also includes the fruit of this plant. To represent the convergent synthesis in this study, three fragments are shown flowing from three rivers, converging in a lake where mucocin is formed. Furthermore, oxypalladation is depicted as a precursor passing through a tunnel. The coordination of palladium to the olefinic portion is illustrated by an Amazon river dolphin. More information can be found in the Research Article by H. Makabe and co-workers (DOI: 10.1002/ejoc.202500990).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 2","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejoc.70313","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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":"https://doi.org/10.1002/ejoc.202501209","url":null,"abstract":"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 <jats:italic>C</jats:italic> ‐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) <jats:sub>6</jats: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%).","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-17","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}
Under the catalysis of Pd 2 (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":"https://doi.org/10.1002/ejoc.202501126","url":null,"abstract":"Under the catalysis of Pd <jats:sub>2</jats:sub> (dba) <jats:sub>3</jats:sub> (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.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-16","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}
Xufei Duan, Zhonghao Han, Jiajun Zhang, Lifang Liu, Hongwei Chen, Yiqin Zhou, Ran Lin, Binbin Huang, Rongbiao Tong, Liyan Song
Achmatowicz rearrangement (AchR) has been widely used for the synthesis of various heterocyclic building blocks and natural products. N-bromo succinimide (NBS) was often used as a stochiometric oxidation reagent to promote AchR with many synthetic advantages; however, the generation of stochiometric succinimide as the byproduct is undesirable from the perspective of green chemistry and occasionally complicates the purification process in a large scale. Herein, we report the development of catalytic NBS (5 mol%) for AchR with oxone as the terminal oxidant, which generates only small amount (5%) of the succinimide byproduct and substochiometric K2SO4 (95%). The 24-times reduction of NBS (from 1.2 equivalent to catalytic 5 mol%) substantially improves the greenness of this protocol and greatly eases the purification of the AchR product. The efficiency and utility of this protocol are consistently superior to the NBS condition and demonstrated with the broad substrate scope (21 examples including steroid substrates), excellent yields, and scalability. Moreover, mechanistic studies suggested that NBS initiated the AchR reaction and the concomitant bromide byproduct could be oxidized by oxone into reactive brominating species in the form of NBS and/or HOBr for subsequent AchR reaction. We believe this new catalytic NBS protocol will find wide applications in organic synthesis.
{"title":"Catalytic N-Bromo Succinimide Enables Achmatowicz Rearrangement with Oxone","authors":"Xufei Duan, Zhonghao Han, Jiajun Zhang, Lifang Liu, Hongwei Chen, Yiqin Zhou, Ran Lin, Binbin Huang, Rongbiao Tong, Liyan Song","doi":"10.1002/ejoc.202501135","DOIUrl":"https://doi.org/10.1002/ejoc.202501135","url":null,"abstract":"Achmatowicz rearrangement (AchR) has been widely used for the synthesis of various heterocyclic building blocks and natural products. <i>N</i>-bromo succinimide (NBS) was often used as a stochiometric oxidation reagent to promote AchR with many synthetic advantages; however, the generation of stochiometric succinimide as the byproduct is undesirable from the perspective of green chemistry and occasionally complicates the purification process in a large scale. Herein, we report the development of catalytic NBS (5 mol%) for AchR with oxone as the terminal oxidant, which generates only small amount (5%) of the succinimide byproduct and substochiometric K<sub>2</sub>SO<sub>4</sub> (95%). The 24-times reduction of NBS (from 1.2 equivalent to catalytic 5 mol%) substantially improves the greenness of this protocol and greatly eases the purification of the AchR product. The efficiency and utility of this protocol are consistently superior to the NBS condition and demonstrated with the broad substrate scope (21 examples including steroid substrates), excellent yields, and scalability. Moreover, mechanistic studies suggested that NBS initiated the AchR reaction and the concomitant bromide byproduct could be oxidized by oxone into reactive brominating species in the form of NBS and/or HOBr for subsequent AchR reaction. We believe this new catalytic NBS protocol will find wide applications in organic synthesis.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"30 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972243","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}
Lorenzo Lorenzini, Andrea Barbero, Remi Blieck, Franck Ferreira, Alejandro Perez‐Luna
A new protocol for alkene hydrogermylation with hydrogermanes involving a radical chain‐transfer mechanism initiated by di‐ tert ‐butyl peroxide (DTBP) and CuI in methyl tert ‐butyl ether (MTBE) is disclosed. The method has good generality regarding both appropriate alkene substrate‐types and hydrogermanes, and compares well to other existing protocols, sometimes improving them, while being easy‐to‐implement. The developed system is particularly well‐suited for indenes and allows for the preparation of original 2‐germylated indanes through a previously unexplored approach.
{"title":"Di‐ tert ‐Butyl‐Peroxide–CuI Promoted Radical Hydrogermylation of Alkenes","authors":"Lorenzo Lorenzini, Andrea Barbero, Remi Blieck, Franck Ferreira, Alejandro Perez‐Luna","doi":"10.1002/ejoc.202501041","DOIUrl":"https://doi.org/10.1002/ejoc.202501041","url":null,"abstract":"A new protocol for alkene hydrogermylation with hydrogermanes involving a radical chain‐transfer mechanism initiated by di‐ <jats:italic>tert</jats:italic> ‐butyl peroxide (DTBP) and CuI in methyl <jats:italic>tert</jats:italic> ‐butyl ether (MTBE) is disclosed. The method has good generality regarding both appropriate alkene substrate‐types and hydrogermanes, and compares well to other existing protocols, sometimes improving them, while being easy‐to‐implement. The developed system is particularly well‐suited for indenes and allows for the preparation of original 2‐germylated indanes through a previously unexplored approach.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968400","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 photoredox silylation protocol of N ‐acrylamides with stable hydrosilanes as radical precursors is reported, affording a series of silylated oxindoles in yields up to 87%. This transformation proceeded through a tandem radical addition and cyclization cascade. This protocol is advantageous, as it features broad functional tolerance and mild reaction conditions. The successful late‐stage functionalization of drug hybrids further demonstrated the utility of this method. Mechanistic investigations revealed that the key silyl radical is generated via a crucial synergistic photoredox and hydrogen atom transfer catalytic system.
{"title":"Dual Photoredox/Hydrogen Atom Transfer Catalysis for the Cascade Silylation and Cyclization of N ‐Acrylamides","authors":"Hsin‐Yu Pan, Chen‐Xuan Lin, Bo‐Ying Tsai, Chin‐Yuan Chang, Ya‐Chu Hsieh","doi":"10.1002/ejoc.202501153","DOIUrl":"https://doi.org/10.1002/ejoc.202501153","url":null,"abstract":"A photoredox silylation protocol of <jats:italic>N</jats:italic> ‐acrylamides with stable hydrosilanes as radical precursors is reported, affording a series of silylated oxindoles in yields up to 87%. This transformation proceeded through a tandem radical addition and cyclization cascade. This protocol is advantageous, as it features broad functional tolerance and mild reaction conditions. The successful late‐stage functionalization of drug hybrids further demonstrated the utility of this method. Mechanistic investigations revealed that the key silyl radical is generated via a crucial synergistic photoredox and hydrogen atom transfer catalytic system.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"82 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968402","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}
Jun Zhu, Zhong-Wen Chen, Teng-Yu Huang, Xu-Dong Wang, Yu-Fei Ao, Qi-Qiang Wang, De-Xian Wang
Chalcogen bond (ChB)–based heteroditopic receptors integrating neutral or positively charged thiazole motifs as anion binding sites and glycol chains as cation binding sites into a host framework were synthesized. 1H NMR titration experiments revealed that the neutral receptors showed stronger binding ability for cations than for anions, whereas the protonated receptors demonstrated significantly enhanced anion binding but largely diminished cation association. In solution, the charge–neutral receptors displayed ion-pair binding due to the allosteric effect from the bound cation and anion. Single–crystal X–ray analysis demonstrated the ion pairs are stabilized by the thiazoles through ChB interactions, the glycol chain through ion–dipole interactions, and cation–anion interactions.
{"title":"Chalcogen Bonding Heteroditopic Receptors for Ion-Pair Binding","authors":"Jun Zhu, Zhong-Wen Chen, Teng-Yu Huang, Xu-Dong Wang, Yu-Fei Ao, Qi-Qiang Wang, De-Xian Wang","doi":"10.1002/ejoc.202501180","DOIUrl":"https://doi.org/10.1002/ejoc.202501180","url":null,"abstract":"Chalcogen bond (ChB)–based heteroditopic receptors integrating neutral or positively charged thiazole motifs as anion binding sites and glycol chains as cation binding sites into a host framework were synthesized. <sup>1</sup>H NMR titration experiments revealed that the neutral receptors showed stronger binding ability for cations than for anions, whereas the protonated receptors demonstrated significantly enhanced anion binding but largely diminished cation association. In solution, the charge–neutral receptors displayed ion-pair binding due to the allosteric effect from the bound cation and anion. Single–crystal X–ray analysis demonstrated the ion pairs are stabilized by the thiazoles through ChB interactions, the glycol chain through ion–dipole interactions, and cation–anion interactions.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"21 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962205","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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