Meng Guo , Zhi-Peng Ye , Yong-Qing Ye , Xiao-Qing Chen , Kai Chen , Hua Yang
Selective hydrodefluorination of trifluoromethyl-bearing scaffolds remains challenging due to the unexpected over-defluorination. Herein, we report a photocatalytic chemoselective hydrodefluorination of trifluoromethyl acetamides enabled by readily tuning the wavelength of light irradiation, in which formate serves as both a hydrogen atom transfer (HAT) reagent and an electron donor for the EDA complex. This strategy enables the selective monohydrodefluorination and dihydrodefluorination of the trifluoromethyl unit under mild conditions, accommodating a variety of trifluoroacetamides. Mechanistic investigations disclosed that a wavelength-dependent SET/EDA manipulation is crucial to the chemoselectivity of this defluorination platform.
{"title":"Wavelength-tuned, photocatalytic chemoselective hydrodefluorination","authors":"Meng Guo , Zhi-Peng Ye , Yong-Qing Ye , Xiao-Qing Chen , Kai Chen , Hua Yang","doi":"10.1039/d5qo01012h","DOIUrl":"10.1039/d5qo01012h","url":null,"abstract":"<div><div>Selective hydrodefluorination of trifluoromethyl-bearing scaffolds remains challenging due to the unexpected over-defluorination. Herein, we report a photocatalytic chemoselective hydrodefluorination of trifluoromethyl acetamides enabled by readily tuning the wavelength of light irradiation, in which formate serves as both a hydrogen atom transfer (HAT) reagent and an electron donor for the EDA complex. This strategy enables the selective monohydrodefluorination and dihydrodefluorination of the trifluoromethyl unit under mild conditions, accommodating a variety of trifluoroacetamides. Mechanistic investigations disclosed that a wavelength-dependent SET/EDA manipulation is crucial to the chemoselectivity of this defluorination platform.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6569-6574"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144995804","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}
Yunbi Koh , GaYeon Yoo , Jinsung Tae , Sanghee Lee , Ansoo Lee
A novel photocatalyst-free radical conjugate addition to 2-substituted chromones has been developed, utilizing Hantzsch esters and TMSOTf to efficiently access diverse 2,2-disubstituted chroman-4-ones under mild conditions. Mechanistic studies, including UV–vis spectroscopy and 1H NMR titration, indicate that the reaction proceeds via an electron donor–acceptor (EDA) complex, which is formed in situ through the reaction of TMSOTf with chromones to generate 4-siloxy-1-benzopyrylium salts. This versatile method enables late-stage functionalization of natural chromones, affording structurally diverse scaffolds with promising biological activity. The resulting chroman-4-one derivatives suppress cGAMP-induced immune responses in ISRE assays, whereas their parent chromones enhance these responses. These results highlight chroman-4-ones as promising immunosuppressive scaffolds for therapeutic development.
{"title":"Radical conjugate addition to 2-substituted chromones via an electron donor–acceptor complex","authors":"Yunbi Koh , GaYeon Yoo , Jinsung Tae , Sanghee Lee , Ansoo Lee","doi":"10.1039/d5qo00933b","DOIUrl":"10.1039/d5qo00933b","url":null,"abstract":"<div><div>A novel photocatalyst-free radical conjugate addition to 2-substituted chromones has been developed, utilizing Hantzsch esters and TMSOTf to efficiently access diverse 2,2-disubstituted chroman-4-ones under mild conditions. Mechanistic studies, including UV–vis spectroscopy and <sup>1</sup>H NMR titration, indicate that the reaction proceeds <em>via</em> an electron donor–acceptor (EDA) complex, which is formed <em>in situ</em> through the reaction of TMSOTf with chromones to generate 4-siloxy-1-benzopyrylium salts. This versatile method enables late-stage functionalization of natural chromones, affording structurally diverse scaffolds with promising biological activity. The resulting chroman-4-one derivatives suppress cGAMP-induced immune responses in ISRE assays, whereas their parent chromones enhance these responses. These results highlight chroman-4-ones as promising immunosuppressive scaffolds for therapeutic development.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6519-6527"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145533070","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}
Paula González-Andrés , Alberto Cherubin , Asunción Barbero
Our ongoing research into silyl-Prins cyclizations has now provided a promising solution for the stereoselective synthesis of tetrahydropyrans bearing quaternary centers at C4. Building on the previous success with terminal cyclopropylsilyl alcohols, we now demonstrate that internal cyclopropylsilyl alcohols can also be effectively employed to construct highly substituted tetrahydropyrans. This new approach delivers products featuring both a quaternary center at C4 and a tertiary center at C6 with excellent stereocontrol. These findings not only broaden the scope of silyl-Prins cyclization but also establish a general and efficient strategy for accessing complex oxacyclic architectures with precise stereochemical outcomes.
{"title":"Expanding the silyl-Prins toolbox: selective access to C4-quaternary stereocenters in tetrahydropyrans using internal cyclopropylsilyl alcohols","authors":"Paula González-Andrés , Alberto Cherubin , Asunción Barbero","doi":"10.1039/d5qo00984g","DOIUrl":"10.1039/d5qo00984g","url":null,"abstract":"<div><div>Our ongoing research into silyl-Prins cyclizations has now provided a promising solution for the stereoselective synthesis of tetrahydropyrans bearing quaternary centers at C4. Building on the previous success with terminal cyclopropylsilyl alcohols, we now demonstrate that internal cyclopropylsilyl alcohols can also be effectively employed to construct highly substituted tetrahydropyrans. This new approach delivers products featuring both a quaternary center at C4 and a tertiary center at C6 with excellent stereocontrol. These findings not only broaden the scope of silyl-Prins cyclization but also establish a general and efficient strategy for accessing complex oxacyclic architectures with precise stereochemical outcomes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6513-6518"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144813053","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}
While catalytic asymmetric alkynylation reactions have been extensively studied, the existing examples predominantly focus on the construction of the stereogenic center at the addition site. Here, we disclose a chiral CuI complex-catalysed asymmetric alkynylation reaction of prochiral terminal diynes, which can furnish a diverse array of products with remote alkyne-tethered 1,4-central chirality that is challenging to achieve. Mechanistic studies demonstrate that the initial desymmetrising deprotonation of the terminal diynes mediated by a chiral π-acidic CuI complex plays a crucial role in governing the diastereoselectivity, while the nucleophilic alkynylation step determines the enantiocontrol of the whole process. This strategy could be successfully extended to the kinetic transformation of racemic terminal alkynes. This stepwise asymmetric deprotonation and alkynylation strategy facilitated by a single chiral catalyst provides a robust platform for diastereo- and enantioselective construction of products with challenging-to-achieve rectilinear 1,4-central chirality.
{"title":"Diastereoselective and enantioselective construction of 1,4-nonadjacent alkyne-tethered products through CuI-promoted deprotonation and addition of terminal alkynes","authors":"Jia-Le Zheng , Wan-Hong Yuan , Han-Wen Zheng , Wei Du , Ying-Chun Chen","doi":"10.1039/d5qo00995b","DOIUrl":"10.1039/d5qo00995b","url":null,"abstract":"<div><div>While catalytic asymmetric alkynylation reactions have been extensively studied, the existing examples predominantly focus on the construction of the stereogenic center at the addition site. Here, we disclose a chiral Cu<sup>I</sup> complex-catalysed asymmetric alkynylation reaction of prochiral terminal diynes, which can furnish a diverse array of products with remote alkyne-tethered 1,4-central chirality that is challenging to achieve. Mechanistic studies demonstrate that the initial desymmetrising deprotonation of the terminal diynes mediated by a chiral π-acidic Cu<sup>I</sup> complex plays a crucial role in governing the diastereoselectivity, while the nucleophilic alkynylation step determines the enantiocontrol of the whole process. This strategy could be successfully extended to the kinetic transformation of racemic terminal alkynes. This stepwise asymmetric deprotonation and alkynylation strategy facilitated by a single chiral catalyst provides a robust platform for diastereo- and enantioselective construction of products with challenging-to-achieve rectilinear 1,4-central chirality.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6407-6414"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144898833","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}
Since the re-birth of sulfur-fluoride exchange (SuFEx) chemistry, coined by Sharpless in 2014 as a ‘click’ reaction, the prevalence of sulfur(vi) moieties in medicinal, polymer and materials chemistry has increased significantly. SuFEx and analogous substitution reactions at electrophilic S(vi) reagents are often performed on symmetrical, achiral S(vi) centres. However, when these substitution reactions are applied to chiral S(vi) substrates, often enantioenriched chiral-at-sulfur aza-S(vi) analogues, the stereochemical outcome of the reaction must be considered to obtain the appropriate 3D configuration. In this review, we aim to draw together the stereochemical outcomes and mechanistic understanding of substitution reactions occurring at electrophilic chiral S(vi) reagents to provide support, and potential word of caution, to the growing field. In addition, we review the significant developments in stereocontrolled reactions at S(vi) centres.
{"title":"The stereochemistry of substitution at S(vi)","authors":"Oliver L. Symes , James A. Bull","doi":"10.1039/d5qo01043h","DOIUrl":"10.1039/d5qo01043h","url":null,"abstract":"<div><div>Since the re-birth of sulfur-fluoride exchange (SuFEx) chemistry, coined by Sharpless in 2014 as a ‘click’ reaction, the prevalence of sulfur(<span>vi</span>) moieties in medicinal, polymer and materials chemistry has increased significantly. SuFEx and analogous substitution reactions at electrophilic S(<span>vi</span>) reagents are often performed on symmetrical, achiral S(<span>vi</span>) centres. However, when these substitution reactions are applied to chiral S(<span>vi</span>) substrates, often enantioenriched chiral-at-sulfur aza-S(<span>vi</span>) analogues, the stereochemical outcome of the reaction must be considered to obtain the appropriate 3D configuration. In this review, we aim to draw together the stereochemical outcomes and mechanistic understanding of substitution reactions occurring at electrophilic chiral S(<span>vi</span>) reagents to provide support, and potential word of caution, to the growing field. In addition, we review the significant developments in stereocontrolled reactions at S(<span>vi</span>) centres.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6681-6697"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145533082","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}
In nickel-catalyzed C(sp2)–C(sp3) cross-coupling, employing cost-effective cobalt complexes as co-catalysts presents distinct advantages. The Ni/Co dual-catalyzed reductive coupling of aryl halides and alkyls has emerged as a powerful strategy to form C(sp2)–C(sp3) bonds, yet its detailed mechanistic understanding remains elusive. Herein, we elucidate the mechanism for the reductive coupling between aryl and alkyl electrophiles in the presence of a Ni/CoII(PC) dual catalytic system by density functional theory (DFT). The cobalt catalyst activates alkyl halides via an SN2 oxidative addition pathway, generating a CoIII(Pc)-Alk intermediate, while the nickel catalyst specifically engages aryl halides. The subsequent anti-alkylation step between these intermediates drives the formation of C(sp2)–C(sp3) bonds with high selectivity. These mechanistic insights not only rationalize the enhanced efficiency and high functional-group compatibility of the Ni/Co system but also provide a framework for developing future dual-metal catalytic methodologies. Our findings advance synthetic strategies for constructing complex molecules and highlight the potential of bimetallic catalysis in organic synthesis.
{"title":"Synergistic Ni/Co catalysis in C(sp2)–C(sp3) reductive coupling: a DFT study","authors":"Junjie Liu , Fengjiao Xiao , Weichi Chen , Abing Duan","doi":"10.1039/d5qo00975h","DOIUrl":"10.1039/d5qo00975h","url":null,"abstract":"<div><div>In nickel-catalyzed C(sp<sup>2</sup>)–C(sp<sup>3</sup>) cross-coupling, employing cost-effective cobalt complexes as co-catalysts presents distinct advantages. The Ni/Co dual-catalyzed reductive coupling of aryl halides and alkyls has emerged as a powerful strategy to form C(sp<sup>2</sup>)–C(sp<sup>3</sup>) bonds, yet its detailed mechanistic understanding remains elusive. Herein, we elucidate the mechanism for the reductive coupling between aryl and alkyl electrophiles in the presence of a Ni/Co<sup>II</sup>(PC) dual catalytic system by density functional theory (DFT). The cobalt catalyst activates alkyl halides <em>via</em> an S<sub>N</sub>2 oxidative addition pathway, generating a Co<sup>III</sup>(Pc)-Alk intermediate, while the nickel catalyst specifically engages aryl halides. The subsequent anti-alkylation step between these intermediates drives the formation of C(sp<sup>2</sup>)–C(sp<sup>3</sup>) bonds with high selectivity. These mechanistic insights not only rationalize the enhanced efficiency and high functional-group compatibility of the Ni/Co system but also provide a framework for developing future dual-metal catalytic methodologies. Our findings advance synthetic strategies for constructing complex molecules and highlight the potential of bimetallic catalysis in organic synthesis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6506-6512"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145533069","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}
Aditya K. Sahay , Callum S. Begg , Xiurong Zhang , James. A. Bull , Alan C. Spivey
Azetidines have gained traction in drug discovery for their ability to introduce conformational constraint and modulate physiochemical properties. Strategies that enable their selective functionalization or controlled expansion into more complex scaffolds provide opportunities for molecular diversification to rapidly access new chemical space. Subjecting 2,2-disubstituted azetidines to amide coupling with carboxylic acids is found to effect either N-acylation or ring expansion to spiro and 6,6-disubstituted 5,6-dihydro-4H-1,3-oxazine, dependent on reaction conditions. A diverse range of topologically interesting heterocycles, which hold significant potential for pharmaceutical screening, have been prepared using this divergent reaction manifold. A mechanistic framework, supported by additive screening and trapping experiments, is presented to account for the ring expansion and racemization that accompanies these transformations when the substrate allows formation of a ring-opened azafulvenium intermediate.
{"title":"Structurally divergent reactivity of 2,2-disubstituted azetidines – mechanistic insights and stereochemical implications of amide coupling and ring expansion to 5,6-dihydro-4H-1,3-oxazines","authors":"Aditya K. Sahay , Callum S. Begg , Xiurong Zhang , James. A. Bull , Alan C. Spivey","doi":"10.1039/d5qo00804b","DOIUrl":"10.1039/d5qo00804b","url":null,"abstract":"<div><div>Azetidines have gained traction in drug discovery for their ability to introduce conformational constraint and modulate physiochemical properties. Strategies that enable their selective functionalization or controlled expansion into more complex scaffolds provide opportunities for molecular diversification to rapidly access new chemical space. Subjecting 2,2-disubstituted azetidines to amide coupling with carboxylic acids is found to effect either <em>N</em>-acylation or ring expansion to spiro and 6,6-disubstituted 5,6-dihydro-4<em>H</em>-1,3-oxazine, dependent on reaction conditions. A diverse range of topologically interesting heterocycles, which hold significant potential for pharmaceutical screening, have been prepared using this divergent reaction manifold. A mechanistic framework, supported by additive screening and trapping experiments, is presented to account for the ring expansion and racemization that accompanies these transformations when the substrate allows formation of a ring-opened azafulvenium intermediate.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6556-6563"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911120","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}
Lucía Sánchez-Jiménez , Adrián Gargantiel , Manuel A. Fernández-Rodríguez , Patricia García-García
Compounds containing tricyclic bridgehead carbon centers are privileged structures in drug discovery. In this work, two different polycyclic scaffolds containing this substructure have been accessed by divergent gold-catalyzed cycloisomerizations of o-cyclopropylidenemethyl-o′-alkynylbiaryls. Selectivity towards one or the other scaffold is mainly controlled by temperature. The electronic nature of the arene group at the alkyne also plays a significant role, which is explained based on the proposed mechanism.
{"title":"Divergent synthesis of two polycyclic frameworks containing tricyclic bridgehead carbon centers by gold-catalyzed cycloisomerization of o-cyclopropylidenemethyl-o′-alkynylbiaryls","authors":"Lucía Sánchez-Jiménez , Adrián Gargantiel , Manuel A. Fernández-Rodríguez , Patricia García-García","doi":"10.1039/d5qo00816f","DOIUrl":"10.1039/d5qo00816f","url":null,"abstract":"<div><div>Compounds containing tricyclic bridgehead carbon centers are privileged structures in drug discovery. In this work, two different polycyclic scaffolds containing this substructure have been accessed by divergent gold-catalyzed cycloisomerizations of <em>o</em>-cyclopropylidenemethyl-<em>o</em>′-alkynylbiaryls. Selectivity towards one or the other scaffold is mainly controlled by temperature. The electronic nature of the arene group at the alkyne also plays a significant role, which is explained based on the proposed mechanism.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6499-6505"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144898772","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}
Shengbiao Yang , Xiaochen Wang , Lan Bao , Tianzhen Wang , Lingang Wu , Qingmin Wang
Ketones are widely recognized as privileged structural motifs in organic synthesis due to their unique dual reactivity profile, serving as versatile electrophiles in numerous carbon–carbon and carbon–heteroatom bond-forming transformations. Their ubiquitous presence in pharmacologically active compounds, advanced materials, and agrochemicals further underscores their synthetic importance. Consequently, the design of novel catalytic platforms enabling efficient construction of structurally diverse ketones from readily available precursors represents a significant challenge in contemporary synthetic methodology. Carboxylic acids and derivatives, owing to their natural abundance, low cost, and exceptional structural variability, are an ideal class of starting materials for such transformations. The integration of these compounds with photocatalysis enables their transformation into ketones through radical-based reaction strategies, offering distinct advantages over conventional two-electron reaction systems by circumventing their inherent limitations.
{"title":"Photocatalytic ketone synthesis: recent advances in radical-based approaches from carboxylic acids and derivatives","authors":"Shengbiao Yang , Xiaochen Wang , Lan Bao , Tianzhen Wang , Lingang Wu , Qingmin Wang","doi":"10.1039/d5qo01059d","DOIUrl":"10.1039/d5qo01059d","url":null,"abstract":"<div><div>Ketones are widely recognized as privileged structural motifs in organic synthesis due to their unique dual reactivity profile, serving as versatile electrophiles in numerous carbon–carbon and carbon–heteroatom bond-forming transformations. Their ubiquitous presence in pharmacologically active compounds, advanced materials, and agrochemicals further underscores their synthetic importance. Consequently, the design of novel catalytic platforms enabling efficient construction of structurally diverse ketones from readily available precursors represents a significant challenge in contemporary synthetic methodology. Carboxylic acids and derivatives, owing to their natural abundance, low cost, and exceptional structural variability, are an ideal class of starting materials for such transformations. The integration of these compounds with photocatalysis enables their transformation into ketones through radical-based reaction strategies, offering distinct advantages over conventional two-electron reaction systems by circumventing their inherent limitations.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6662-6680"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144840267","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}
Wangjian Fang , Xin Li , Audrey Nathania Johan , Yimin Zhang , Guoqiang Jiang , Andrew C.-H. Sue
Triphenylamine[3]arenes (TPA[3]s) are a novel class of macrocyclic scaffolds with remarkable potential in supramolecular chemistry. In this study, we present a streamlined synthesis of TPA[3]s featuring meta- or para-substituted bromophenyl or ester moieties on the nitrogen-bridging units via a BF3·Et2O-catalysed one-pot Friedel–Crafts reaction, achieving up to near-quantitative yields within five minutes. These labile substituents at the equatorial positions enable efficient post-cyclisation functionalisation under mild conditions, facilitating the introduction of diverse functional groups, including nitrophenyl, pyrene, terpyridine, and carboxylic acid units. These meta-functionalised TPA[3]s exhibit exceptional structural flexibility, enabling their use as tri-topic building blocks for the construction of metal–organic cages (MOCs) through a subcomponent self-assembly strategy. By precisely tuning ligand denticity and metal coordination, we synthesised a diverse range of MOCs, including tetrahedral M4L4 cages, dimeric M3L2 assemblies, and octahedral M6L4 architectures. These results demonstrate the versatility of TPA[3] scaffolds in advancing hierarchical supramolecular assembly and highlight their potential for creating structurally diverse and well-defined supramolecular architectures.
{"title":"Streamlined synthesis of meta- or para-substituted triphenylamine[3]arenes and their hierarchical assembly into polyhedral cages","authors":"Wangjian Fang , Xin Li , Audrey Nathania Johan , Yimin Zhang , Guoqiang Jiang , Andrew C.-H. Sue","doi":"10.1039/d5qo01089f","DOIUrl":"10.1039/d5qo01089f","url":null,"abstract":"<div><div>Triphenylamine[3]arenes (TPA[3]s) are a novel class of macrocyclic scaffolds with remarkable potential in supramolecular chemistry. In this study, we present a streamlined synthesis of TPA[3]s featuring <em>meta</em>- or <em>para</em>-substituted bromophenyl or ester moieties on the nitrogen-bridging units <em>via</em> a BF<sub>3</sub>·Et<sub>2</sub>O-catalysed one-pot Friedel–Crafts reaction, achieving up to near-quantitative yields within five minutes. These labile substituents at the equatorial positions enable efficient post-cyclisation functionalisation under mild conditions, facilitating the introduction of diverse functional groups, including nitrophenyl, pyrene, terpyridine, and carboxylic acid units. These <em>meta</em>-functionalised TPA[3]s exhibit exceptional structural flexibility, enabling their use as tri-topic building blocks for the construction of metal–organic cages (MOCs) through a subcomponent self-assembly strategy. By precisely tuning ligand denticity and metal coordination, we synthesised a diverse range of MOCs, including tetrahedral M<sub>4</sub>L<sub>4</sub> cages, dimeric M<sub>3</sub>L<sub>2</sub> assemblies, and octahedral M<sub>6</sub>L<sub>4</sub> architectures. These results demonstrate the versatility of TPA[3] scaffolds in advancing hierarchical supramolecular assembly and highlight their potential for creating structurally diverse and well-defined supramolecular architectures.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 23","pages":"Pages 6594-6601"},"PeriodicalIF":0.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144995653","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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