Pub Date : 2025-09-05Epub Date: 2025-06-23DOI: 10.1039/d5qo00618j
Kemeng Zhang , Shuodan Ding , Jie Zhou , Xinyu Zhou , Ge Wu , XinLei Wu
Bunte salts are frequently utilized as effective thiolation reagents for constructing thioethers. In this study, we discovered that Bunte salts could also serve as mediators to enable the oxidative C–H sulfonation of alkenes with sodium sulfinates. Mechanistically, alkyl sulfides are generated as key intermediates, which undergo an unusual oxidative elimination to give the corresponding products. These tandem addition–elimination reactions allow for the conversion of various styrenes and α-alkyl styrenes into vinyl and allylic sulfones in useful to excellent yields.
{"title":"Bunte salt-mediated sulfonation of alkenes with sodium sulfinates†","authors":"Kemeng Zhang , Shuodan Ding , Jie Zhou , Xinyu Zhou , Ge Wu , XinLei Wu","doi":"10.1039/d5qo00618j","DOIUrl":"10.1039/d5qo00618j","url":null,"abstract":"<div><div>Bunte salts are frequently utilized as effective thiolation reagents for constructing thioethers. In this study, we discovered that Bunte salts could also serve as mediators to enable the oxidative C–H sulfonation of alkenes with sodium sulfinates. Mechanistically, alkyl sulfides are generated as key intermediates, which undergo an unusual oxidative elimination to give the corresponding products. These tandem addition–elimination reactions allow for the conversion of various styrenes and α-alkyl styrenes into vinyl and allylic sulfones in useful to excellent yields.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5616-5621"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-06-20DOI: 10.1039/d5qo00785b
Jiantao Zhang , Renhua Su , Weibing Liu
In recent years, radical-mediated functionalization of olefins has gradually become a research hotspot in the field of organic synthesis due to its high reactivity, excellent regioselectivity, and wide substrate applicability. Compared to traditional ionic pathways, radical strategies effectively avoid compatibility issues with some functional groups through modes, such as photocatalysis, electrocatalysis, or chemical initiation, and provide new pathways for the diversified conversion of olefins, such as bifunctional, hydrogen functionalization, and cyclization reactions. Among them, tert-butyl hydroperoxide (TBHP) plays multiple roles in synthetic chemistry as an efficient and inexpensive oxidant and radical precursor: it is not only a classic initiator of radical chain reactions but also a source of tert-butyl peroxide, tert-butyl oxygen, methyl, oxygen, hydrogen, or hydroxyl groups. The unique capacity to generate controllable radical species establishes TBHP as an indispensable platform for advancing green synthetic methodologies, empowering pharmaceutical innovation and deciphering fundamental reaction mechanisms. In this review, we summarize the recent progress in TBHP-enabled transformations of alkenes, which are categorized as peroxidation, carbonylation, epoxidation, etherification, hydrogenation, and hydroxylation. Within each category, representative studies are presented and discussed in terms of mechanistic insights and substrate scope expansion.
{"title":"Radical di- and multi-functionalization of alkenes: recent advances in diverse reaction modes utilizing TBHP as reactants","authors":"Jiantao Zhang , Renhua Su , Weibing Liu","doi":"10.1039/d5qo00785b","DOIUrl":"10.1039/d5qo00785b","url":null,"abstract":"<div><div>In recent years, radical-mediated functionalization of olefins has gradually become a research hotspot in the field of organic synthesis due to its high reactivity, excellent regioselectivity, and wide substrate applicability. Compared to traditional ionic pathways, radical strategies effectively avoid compatibility issues with some functional groups through modes, such as photocatalysis, electrocatalysis, or chemical initiation, and provide new pathways for the diversified conversion of olefins, such as bifunctional, hydrogen functionalization, and cyclization reactions. Among them, <em>tert</em>-butyl hydroperoxide (TBHP) plays multiple roles in synthetic chemistry as an efficient and inexpensive oxidant and radical precursor: it is not only a classic initiator of radical chain reactions but also a source of <em>tert</em>-butyl peroxide, <em>tert</em>-butyl oxygen, methyl, oxygen, hydrogen, or hydroxyl groups. The unique capacity to generate controllable radical species establishes TBHP as an indispensable platform for advancing green synthetic methodologies, empowering pharmaceutical innovation and deciphering fundamental reaction mechanisms. In this review, we summarize the recent progress in TBHP-enabled transformations of alkenes, which are categorized as peroxidation, carbonylation, epoxidation, etherification, hydrogenation, and hydroxylation. Within each category, representative studies are presented and discussed in terms of mechanistic insights and substrate scope expansion.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5683-5716"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-06-26DOI: 10.1039/d5qo00671f
Jia-Tian Liu , Jiashu Liu , Qi-Long Hu , Jian Li
Herein, we disclosed a dual-functionalization of tryptophan derivatives at the C2 and C4 positions of the indole ring through a palladium-catalyzed cascade C–H activation. This step-economical protocol features operational simplicity under mild conditions, achieving concurrent aryl and acetoxy group installation in one pot, making it a straightforward approach to efficiently synthesize highly decorated tryptophan derivatives. Furthermore, gram-scale synthesis and further transformation were also feasible, demonstrating the robustness of this method.
{"title":"One-pot C2-arylation and C4-acetoxylation of tryptophan derivatives via palladium-catalyzed tandem C–H activation†","authors":"Jia-Tian Liu , Jiashu Liu , Qi-Long Hu , Jian Li","doi":"10.1039/d5qo00671f","DOIUrl":"10.1039/d5qo00671f","url":null,"abstract":"<div><div>Herein, we disclosed a dual-functionalization of tryptophan derivatives at the C2 and C4 positions of the indole ring through a palladium-catalyzed cascade C–H activation. This step-economical protocol features operational simplicity under mild conditions, achieving concurrent aryl and acetoxy group installation in one pot, making it a straightforward approach to efficiently synthesize highly decorated tryptophan derivatives. Furthermore, gram-scale synthesis and further transformation were also feasible, demonstrating the robustness of this method.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5591-5596"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144488799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Boron-containing derivatives have numerous applications in medicinal, industrial, and synthetic chemistry. Considering this, a new, mild, catalyst-free, additive-free, base-assisted one-step robust method has been reported for the efficient synthesis of valuable 1,2-oxaborole derivatives via borylation of propynols using only cesium carbonate as a mild base. The reaction proceeds under mild conditions and demonstrates broad substrate scope and high functional group tolerance, making it suitable for a wide range of propargylic alcohols. Mechanistic investigations reveal that this method proceeds through a non-radical pathway.
{"title":"Synthesis of 1,2-oxaborole via base-mediated borylation of propynols†","authors":"Sumit Ghosh , Sudip Laru , Mukta Singsardar , Alakananda Hajra","doi":"10.1039/d5qo00709g","DOIUrl":"10.1039/d5qo00709g","url":null,"abstract":"<div><div>Boron-containing derivatives have numerous applications in medicinal, industrial, and synthetic chemistry. Considering this, a new, mild, catalyst-free, additive-free, base-assisted one-step robust method has been reported for the efficient synthesis of valuable 1,2-oxaborole derivatives <em>via</em> borylation of propynols using only cesium carbonate as a mild base. The reaction proceeds under mild conditions and demonstrates broad substrate scope and high functional group tolerance, making it suitable for a wide range of propargylic alcohols. Mechanistic investigations reveal that this method proceeds through a non-radical pathway.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5597-5602"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144334889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-05-13DOI: 10.1039/d5qo00087d
Sophia Thiele , Michael Giffin , Matthieu Wendling , Daniel Görl , Christopher J. G. Plummer , Holger Frauenrath
Benzenetricarboxamide (BTA) derivatives are versatile compounds widely employed as nucleating agents in commercial semicrystalline plastics and as supramolecular ligands in self-assembling telechelic polymer-based organogels, hydrogels, and bulk elastomers. However, their effectiveness as supramolecular modifiers is typically limited to low-molar-mass apolar polymers. Here, we report the supramolecular aggregation of a BTA-end-functionalized semicrystalline aliphatic polyester with a number-average molar mass several times its entanglement molar mass, blended with a matching low-molar-mass BTA additive. In these blends, the BTA end groups and additive co-assemble to form a new phase comprising a network of polymer-bridged nanofibrils. This network gives rise to a high-melt-strength rubbery regime that is absent from the pure telechelic polyester but extends to temperatures well above its melting point in the blends. Moreover, the nanofibrils prove to be highly efficient nucleating agents for crystallization of the polyester, significantly outperforming bulk additive precipitates. Our findings hence demonstrate that the co-assembly of polymer end groups with a low-molar-mass additive may facilitate supramolecular aggregate formation in polymer matrices where end-modification alone is insufficient, leading to materials with increased melt strength, crystallization rates, thermal dimensional stability, and valuable benefits for industrial applications.
{"title":"Polymer-bridged nanofibrils in a high-molar-mass polyester via co-assembly of benzenetricarboxamide end groups and an additive†","authors":"Sophia Thiele , Michael Giffin , Matthieu Wendling , Daniel Görl , Christopher J. G. Plummer , Holger Frauenrath","doi":"10.1039/d5qo00087d","DOIUrl":"10.1039/d5qo00087d","url":null,"abstract":"<div><div>Benzenetricarboxamide (BTA) derivatives are versatile compounds widely employed as nucleating agents in commercial semicrystalline plastics and as supramolecular ligands in self-assembling telechelic polymer-based organogels, hydrogels, and bulk elastomers. However, their effectiveness as supramolecular modifiers is typically limited to low-molar-mass apolar polymers. Here, we report the supramolecular aggregation of a BTA-end-functionalized semicrystalline aliphatic polyester with a number-average molar mass several times its entanglement molar mass, blended with a matching low-molar-mass BTA additive. In these blends, the BTA end groups and additive co-assemble to form a new phase comprising a network of polymer-bridged nanofibrils. This network gives rise to a high-melt-strength rubbery regime that is absent from the pure telechelic polyester but extends to temperatures well above its melting point in the blends. Moreover, the nanofibrils prove to be highly efficient nucleating agents for crystallization of the polyester, significantly outperforming bulk additive precipitates. Our findings hence demonstrate that the co-assembly of polymer end groups with a low-molar-mass additive may facilitate supramolecular aggregate formation in polymer matrices where end-modification alone is insufficient, leading to materials with increased melt strength, crystallization rates, thermal dimensional stability, and valuable benefits for industrial applications.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5395-5413"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-08-19DOI: 10.1039/d5qo01111f
Axel Leblond , Érick Caique Santos Costa , Karine Leblanc , Edmond Gravel , Jean-François Gallard , Mehdi A. Beniddir , Erwan Poupon
Haouamines are highly constrained marine alkaloids possessing a unique in nature skeleton. The high degree of complexity of such alkaloids raises questions about their chemical assembly. This is addressed in this paper in which we propose a biomimetic scenario corroborated experimentally by a fine study of the classical Chichibabin pyridine synthesis, especially in its “abnormal” oxidative version. Finely tuned reductive conditions and mechanistic investigations permit the concise obtention of an advanced and challenging intermediate that we coined “pre-haouamine”.
{"title":"Bypassing the abnormal Chichibabin reaction dead-end provides a biomimetic access to pre-haouamine","authors":"Axel Leblond , Érick Caique Santos Costa , Karine Leblanc , Edmond Gravel , Jean-François Gallard , Mehdi A. Beniddir , Erwan Poupon","doi":"10.1039/d5qo01111f","DOIUrl":"10.1039/d5qo01111f","url":null,"abstract":"<div><div>Haouamines are highly constrained marine alkaloids possessing a unique in nature skeleton. The high degree of complexity of such alkaloids raises questions about their chemical assembly. This is addressed in this paper in which we propose a biomimetic scenario corroborated experimentally by a fine study of the classical Chichibabin pyridine synthesis, especially in its “abnormal” <em>oxidative</em> version. Finely tuned <em>reductive</em> conditions and mechanistic investigations permit the concise obtention of an advanced and challenging intermediate that we coined “<em>pre</em>-haouamine”.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5372-5378"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-05-30DOI: 10.1039/d5qo00677e
Chunxiao Nong , Kun He , Yingguo Jiang , Fan Zhu , Mingquan Yuan , Jingbo Chen , Yi Jin
Herein, we report a K2S2O8-mediated metal-free radical dehydrogenative cross-coupling reaction that achieves direct C(sp2)–H/C(sp3)–H radical–radical coupling between N,N-dimethylenaminones and glycine derivatives. This reaction efficiently proceeds under oxidative conditions via a single-electron transfer (SET) mechanism, generating both enaminone radicals and α-amino radicals for subsequent coupling. This methodology enables one-step synthesis of 31 structurally diverse 2,3-dicarbonylquinoline derivatives, including 2,3-benzoylquinolines, 2,3-diester quinolines, and 2-ester-3-acylquinolines. This protocol establishes a robust foundation for future applications of such 2,3-dicarbonylquinoline compounds.
{"title":"Cross-dehydrogenative radical coupling enabled by K2S2O8: efficient synthesis of 2,3-dicarbonyl quinolines from enaminones and glycine derivatives†","authors":"Chunxiao Nong , Kun He , Yingguo Jiang , Fan Zhu , Mingquan Yuan , Jingbo Chen , Yi Jin","doi":"10.1039/d5qo00677e","DOIUrl":"10.1039/d5qo00677e","url":null,"abstract":"<div><div>Herein, we report a K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-mediated metal-free radical dehydrogenative cross-coupling reaction that achieves direct C(sp<sup>2</sup>)–H/C(sp<sup>3</sup>)–H radical–radical coupling between <em>N</em>,<em>N</em>-dimethylenaminones and glycine derivatives. This reaction efficiently proceeds under oxidative conditions <em>via</em> a single-electron transfer (SET) mechanism, generating both enaminone radicals and α-amino radicals for subsequent coupling. This methodology enables one-step synthesis of 31 structurally diverse 2,3-dicarbonylquinoline derivatives, including 2,3-benzoylquinolines, 2,3-diester quinolines, and 2-ester-3-acylquinolines. This protocol establishes a robust foundation for future applications of such 2,3-dicarbonylquinoline compounds.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5430-5437"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-06-11DOI: 10.1039/d5qo00519a
Siddhartha Kumar Senapati , Tapashi Das , Animesh Das
Hexafluoroisopropanol (HFIP)-mediated one-pot tandem reduction of quinolines to tetrahydroquinolines followed by reductive alkylation by the aldehyde has been demonstrated through H-bonding network-enabled substrate activation. This step-economical synthetic approach is well suited for late-stage functionalization of complex bioactive molecules. The reaction is highly chemoselective and tolerates a wide range of reducible-sensitive functional groups. The current reductive N-alkylation approach was also successfully utilized to synthesize novel tricyclic oxazino-fused-tetrahydroquinoline/benzoxazine compounds via tandem reductive cyclization of 1-aryl-2-(8-quinolinyloxy) ethanones and synthesis of lilolidine derivatives through the reductive N-alkylation of quinoline followed by a dehydration cyclization sequence. The scope of the reaction has been further extended to C-functionalized N-alkylated THQ derivatives in a one-pot by using para-quinone methides (p-QMs) or nitroolefins as alkylating precursors. The elucidation of an underlying mechanism was achieved through a combination of several control experiments, kinetic studies, and isotopic labeling experiments.
{"title":"Tandem reductive alkylation of quinolines to functionalized tetrahydroquinolines enabled by HFIP†","authors":"Siddhartha Kumar Senapati , Tapashi Das , Animesh Das","doi":"10.1039/d5qo00519a","DOIUrl":"10.1039/d5qo00519a","url":null,"abstract":"<div><div>Hexafluoroisopropanol (HFIP)-mediated one-pot tandem reduction of quinolines to tetrahydroquinolines followed by reductive alkylation by the aldehyde has been demonstrated through H-bonding network-enabled substrate activation. This step-economical synthetic approach is well suited for late-stage functionalization of complex bioactive molecules. The reaction is highly chemoselective and tolerates a wide range of reducible-sensitive functional groups. The current reductive <em>N</em>-alkylation approach was also successfully utilized to synthesize novel tricyclic oxazino-fused-tetrahydroquinoline/benzoxazine compounds <em>via</em> tandem reductive cyclization of 1-aryl-2-(8-quinolinyloxy) ethanones and synthesis of lilolidine derivatives through the reductive <em>N</em>-alkylation of quinoline followed by a dehydration cyclization sequence. The scope of the reaction has been further extended to <em>C</em>-functionalized <em>N</em>-alkylated THQ derivatives in a one-pot by using <em>para</em>-quinone methides (<em>p</em>-QMs) or nitroolefins as alkylating precursors. The elucidation of an underlying mechanism was achieved through a combination of several control experiments, kinetic studies, and isotopic labeling experiments.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5582-5590"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-06-18DOI: 10.1039/d5qo00790a
Shuai Qiu , Yuexia Dong , Wan Xu , Sheng Zhang , Chunli Li , Hua Wang
Three new thiophene/selenophene-based S/Se-[7]helicenes were efficiently synthesized via intermolecular McMurry and oxidative photocyclization reactions. Their helical structures were confirmed through single-crystal analysis. Additionally, these [7]helicenes exhibited notable circularly polarized phosphorescence at 77 K. Theoretical calculations show that both intersystem crossing channels and spin–orbit coupling constants are increased due to the heavy atom effect.
{"title":"Sulfur/selenium atom-incorporated hetero[7]helicenes for low-temperature circularly polarized phosphorescence†","authors":"Shuai Qiu , Yuexia Dong , Wan Xu , Sheng Zhang , Chunli Li , Hua Wang","doi":"10.1039/d5qo00790a","DOIUrl":"10.1039/d5qo00790a","url":null,"abstract":"<div><div>Three new thiophene/selenophene-based S/Se-[7]helicenes were efficiently synthesized <em>via</em> intermolecular McMurry and oxidative photocyclization reactions. Their helical structures were confirmed through single-crystal analysis. Additionally, these [7]helicenes exhibited notable circularly polarized phosphorescence at 77 K. Theoretical calculations show that both intersystem crossing channels and spin–orbit coupling constants are increased due to the heavy atom effect.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5559-5565"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-05Epub Date: 2025-06-11DOI: 10.1039/d5qo00794a
Lin Wan , Yude Ji , Zikang Ma , Chengguo Yan , Weifan Wang , Gang Zhang
Planar and positively curved carbonyl-bridged triphenylamine derivatives with five- and six-membered rings around the central nitrogen atom have been extensively studied. However, the incorporation of seven-membered rings to form negatively curved carbonyl-bridged triphenylamine derivatives is still scarce. Herein, we report the synthesis of a negatively curved carbonyl-bridged triphenylamine compound bearing double hexagonal rings and a heptagonal ring around the central nitrogen atom. The peripheral double bond of the heptagonal ring can be oxidized to form an adjacent diketone compound with room temperature phosphorescence. Naphthalene and quinoxaline units can be fused to the seven-membered ring to give saddle-shaped derivatives, which can assemble with C60 in a 1 : 1 ratio in toluene, with different binding constants depending on the fused units.
{"title":"A negatively curved carbonyl-bridged triphenylamine†","authors":"Lin Wan , Yude Ji , Zikang Ma , Chengguo Yan , Weifan Wang , Gang Zhang","doi":"10.1039/d5qo00794a","DOIUrl":"10.1039/d5qo00794a","url":null,"abstract":"<div><div>Planar and positively curved carbonyl-bridged triphenylamine derivatives with five- and six-membered rings around the central nitrogen atom have been extensively studied. However, the incorporation of seven-membered rings to form negatively curved carbonyl-bridged triphenylamine derivatives is still scarce. Herein, we report the synthesis of a negatively curved carbonyl-bridged triphenylamine compound bearing double hexagonal rings and a heptagonal ring around the central nitrogen atom. The peripheral double bond of the heptagonal ring can be oxidized to form an adjacent diketone compound with room temperature phosphorescence. Naphthalene and quinoxaline units can be fused to the seven-membered ring to give saddle-shaped derivatives, which can assemble with C<sub>60</sub> in a 1 : 1 ratio in toluene, with different binding constants depending on the fused units.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5533-5539"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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