Natalia Fernández-Labandeira,Patricia Remón,Raúl Castellano,María Touriño-Pardo,Marcos D. García,Uwe Pischel,Arturo Blanco-Gómez,Carlos Peinador
Enforced chromophore proximity provides a powerful molecular design principle to reshape excited-state interactions and tune emission. In this work, we report the optical properties of two self-assembled cyclophanes in which the interplanar distance between the longitudinal bispyridinium chromophores is sufficiently short to promote intramolecular interactions. Both cyclophanes were efficiently synthesized through acid-catalyzed hydrazone condensation in water without the need for a templating effect, highlighting their high preorganization for cyclization. Photophysical studies in acetonitrile revealed clear excited-state interchromophoric interactions in both systems. The cyclophane containing the more conjugated bispyridinium unit (o-REx4+) displayed a pronounced red-shifted emission (91 nm) and a nearly ninefold increase in emission efficiency relative to its monomeric counterpart. In contrast, chromophoric interaction in the less conjugated cyclophane (o-R4+) induced fluorescence of an otherwise non-emissive bispyridinium chromophore. The emissions are strongly quenched in water, however, complexation with cucurbit[8]uril (CB[8]) restores the fluorescence of both cyclophanes through the formation of stable ring-in-ring host–guest complexes. These results highlight an efficient synthetic approach to highly preorganized cyclophanes and demonstrate how solvent effects and CB[8] complexation can be exploited to modulate and recover the fluorescence of intramolecular chromophore dimers.
{"title":"Self-assembled hydrazone-derived macrocycles show cucurbit[8]uril-assisted tunable excimer-like emission","authors":"Natalia Fernández-Labandeira,Patricia Remón,Raúl Castellano,María Touriño-Pardo,Marcos D. García,Uwe Pischel,Arturo Blanco-Gómez,Carlos Peinador","doi":"10.1039/d6qo00793g","DOIUrl":"https://doi.org/10.1039/d6qo00793g","url":null,"abstract":"Enforced chromophore proximity provides a powerful molecular design principle to reshape excited-state interactions and tune emission. In this work, we report the optical properties of two self-assembled cyclophanes in which the interplanar distance between the longitudinal bispyridinium chromophores is sufficiently short to promote intramolecular interactions. Both cyclophanes were efficiently synthesized through acid-catalyzed hydrazone condensation in water without the need for a templating effect, highlighting their high preorganization for cyclization. Photophysical studies in acetonitrile revealed clear excited-state interchromophoric interactions in both systems. The cyclophane containing the more conjugated bispyridinium unit (o-REx4+) displayed a pronounced red-shifted emission (91 nm) and a nearly ninefold increase in emission efficiency relative to its monomeric counterpart. In contrast, chromophoric interaction in the less conjugated cyclophane (o-R4+) induced fluorescence of an otherwise non-emissive bispyridinium chromophore. The emissions are strongly quenched in water, however, complexation with cucurbit[8]uril (CB[8]) restores the fluorescence of both cyclophanes through the formation of stable ring-in-ring host–guest complexes. These results highlight an efficient synthetic approach to highly preorganized cyclophanes and demonstrate how solvent effects and CB[8] complexation can be exploited to modulate and recover the fluorescence of intramolecular chromophore dimers.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"144 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chiral synthesis is a core frontier of modern organic chemistry, and the enantioselective construction of non-central chiral skeletons (axial, helical, planar, inherent chirality) remains a key synthetic challenge. As a classic inverse-electron-demand aza-Diels–Alder reaction, the Povarov reaction has evolved from a tool for tetrahydroquinoline synthesis to a versatile platform for diverse chiral molecule construction, while existing reviews lack a systematic summary of its applications in non-central chirality and chiral functional materials. This paper systematically reviews the research progress of the asymmetric Povarov reaction in the synthesis of central, helical, axial, planar and inherently chiral molecules as well as chiral covalent organic frameworks (COFs), focusing on the reaction strategies mediated by catalytic systems such as chiral phosphoric acids and chiral metal phosphates, including core mechanisms like chiral center construction, central-to-axial/helical chirality conversion and desymmetrization. Endowed with advantages such as broad substrate universality, excellent stereoselectivity and mild reaction conditions, this reaction has successfully synthesized structurally diverse chiral compounds with high enantiomeric purity, exhibiting important application value in drug research and development, chiral catalysis, functional materials and other fields. Meanwhile, the reaction still faces bottlenecks including limited compatibility with highly sterically hindered substrates, insufficient universality of catalytic systems, and low industrial translation potential. Finally, the current challenges of this reaction are analyzed, and its development prospects in the design of novel chiral catalysts, total synthesis of natural products and development of functional materials are prospected.
{"title":"Chiral construction based on the Povarov reaction: asymmetric synthesis of diverse chiral molecules and chiral COF materials","authors":"Zhi-Yuan Wang,Chuan-Jun Lu,Ren-Rong Liu","doi":"10.1039/d6qo00787b","DOIUrl":"https://doi.org/10.1039/d6qo00787b","url":null,"abstract":"Chiral synthesis is a core frontier of modern organic chemistry, and the enantioselective construction of non-central chiral skeletons (axial, helical, planar, inherent chirality) remains a key synthetic challenge. As a classic inverse-electron-demand aza-Diels–Alder reaction, the Povarov reaction has evolved from a tool for tetrahydroquinoline synthesis to a versatile platform for diverse chiral molecule construction, while existing reviews lack a systematic summary of its applications in non-central chirality and chiral functional materials. This paper systematically reviews the research progress of the asymmetric Povarov reaction in the synthesis of central, helical, axial, planar and inherently chiral molecules as well as chiral covalent organic frameworks (COFs), focusing on the reaction strategies mediated by catalytic systems such as chiral phosphoric acids and chiral metal phosphates, including core mechanisms like chiral center construction, central-to-axial/helical chirality conversion and desymmetrization. Endowed with advantages such as broad substrate universality, excellent stereoselectivity and mild reaction conditions, this reaction has successfully synthesized structurally diverse chiral compounds with high enantiomeric purity, exhibiting important application value in drug research and development, chiral catalysis, functional materials and other fields. Meanwhile, the reaction still faces bottlenecks including limited compatibility with highly sterically hindered substrates, insufficient universality of catalytic systems, and low industrial translation potential. Finally, the current challenges of this reaction are analyzed, and its development prospects in the design of novel chiral catalysts, total synthesis of natural products and development of functional materials are prospected.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"40 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tong-Shuo Xu,Yi-Ze Bai,Yang-Bo Bi,Jin-De Li,Jing Cao,Zhu Cao,Qing-Hai Deng
A copper-catalyzed dearomative azidation/click cascade reaction of β-naphthol-derived alkynes is reported using a hypervalent iodine azide reagent. This mild and step-economical strategy combines azidation of β-naphthol with intramolecular click cycloaddition under a simple catalytic system, enabling efficient construction of spirocyclic βnaphthalenone-1,2,3-triazole hybrids with a quaternary spiro carbon center. The approach exhibits broad functional group tolerance, excellent yields (up to 99%), gram-scale scalability, and versatile downstream functionalization. This work expands the application of hypervalent iodine reagents in dearomatization and offers a concise route to complex heterocyclic scaffolds with biological potential.
{"title":"Copper-catalyzed dearomative azidation/click cascade reaction of β-naphthol-based phenylalkynes","authors":"Tong-Shuo Xu,Yi-Ze Bai,Yang-Bo Bi,Jin-De Li,Jing Cao,Zhu Cao,Qing-Hai Deng","doi":"10.1039/d6qo00873a","DOIUrl":"https://doi.org/10.1039/d6qo00873a","url":null,"abstract":"A copper-catalyzed dearomative azidation/click cascade reaction of β-naphthol-derived alkynes is reported using a hypervalent iodine azide reagent. This mild and step-economical strategy combines azidation of β-naphthol with intramolecular click cycloaddition under a simple catalytic system, enabling efficient construction of spirocyclic βnaphthalenone-1,2,3-triazole hybrids with a quaternary spiro carbon center. The approach exhibits broad functional group tolerance, excellent yields (up to 99%), gram-scale scalability, and versatile downstream functionalization. This work expands the application of hypervalent iodine reagents in dearomatization and offers a concise route to complex heterocyclic scaffolds with biological potential.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we report the first CPA-catalyzed synthesis of chiral oxime ether derivatives through kinetic resolution of racemic ketones. Racemic tribenzocyclooctanones were condensed with hydroxylamine ethers enantioselectively to afford a series of inherently chiral oxime ethers, as well as enantioenriched tribenzocyclooctanones, which can serve as versatile precursors for the one-step synthesis of various inherently chiral tetraphenylene analogues, including tribenzocyclooctaindoles, tribenzocyclooctaquinolines, and triphenylcyclooctyl ethers. In addition, density functional theory (DFT) calculations disclose a different mechanism from axially chiral oxime formation, in which the nucleophilic attack in the first step determines the inherent chirality of the oxime ether, while the subsequent dehydration process merely governs the configuration of the C═N bond and the overall reaction rate.
{"title":"Kinetic resolution of cyclic racemic ketones through chiral phosphoric acid-catalyzed oxime ether formation","authors":"Yougen Xu,Meiling Chen,Yu Luo,Yuanhang Zhang,Shuang Luo,Qiang Zhu","doi":"10.1039/d6qo00699j","DOIUrl":"https://doi.org/10.1039/d6qo00699j","url":null,"abstract":"Herein, we report the first CPA-catalyzed synthesis of chiral oxime ether derivatives through kinetic resolution of racemic ketones. Racemic tribenzocyclooctanones were condensed with hydroxylamine ethers enantioselectively to afford a series of inherently chiral oxime ethers, as well as enantioenriched tribenzocyclooctanones, which can serve as versatile precursors for the one-step synthesis of various inherently chiral tetraphenylene analogues, including tribenzocyclooctaindoles, tribenzocyclooctaquinolines, and triphenylcyclooctyl ethers. In addition, density functional theory (DFT) calculations disclose a different mechanism from axially chiral oxime formation, in which the nucleophilic attack in the first step determines the inherent chirality of the oxime ether, while the subsequent dehydration process merely governs the configuration of the C═N bond and the overall reaction rate.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"78 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hai Li,Fei Li,Yi-You Zhou,Syed Anis Ali Shah,Wen-Jun Li,Yu-Xiao Ding,Weidong Rao,Shu-Su Shen,Gang Wang,Kai Liu,Shun-Yi Wang
Arylboronic acids are highly valuable structural motifs in synthetic chemistry, medicinal chemistry, materials science, and biomedical applications. However, conventional approaches to arylboronic acids often rely on transition-metal catalysts, prefunctionalized organometallic reagents, or strongly basic conditions, which may limit functional-group tolerance and raise concerns related to cost, metal residues, and environmental sustainability. Herein, we report a visible-light-induced, transition-metal-free and strong-base-free borylation of arylsulfonium salts with tetrahydroxydiboron for the direct preparation of arylboronic acids. This protocol proceeds under mild conditions at room temperature without an external photocatalyst or strong base, highlighting its operational simplicity and green-chemistry potential. A broad range of arylsulfonium salts, including halogenated arenes, biphenyl derivatives, aryl ethers, ester-containing substrates, and drug-derived molecules, are efficiently converted into the corresponding arylboronic acids. Preliminary mechanistic studies are consistent with the possible involvement of substrate interactions and radical species under light irradiation. The combination of visible-light activation, catalyst-free conditions, and broad functional-group compatibility makes this method an attractive platform for sustainable arylboronic acid synthesis and late-stage molecular diversification.
{"title":"Visible-light-induced, transition-metal-free and strong-base-free synthesis of arylboronic acids from arylsulfonium salts","authors":"Hai Li,Fei Li,Yi-You Zhou,Syed Anis Ali Shah,Wen-Jun Li,Yu-Xiao Ding,Weidong Rao,Shu-Su Shen,Gang Wang,Kai Liu,Shun-Yi Wang","doi":"10.1039/d6qo00862c","DOIUrl":"https://doi.org/10.1039/d6qo00862c","url":null,"abstract":"Arylboronic acids are highly valuable structural motifs in synthetic chemistry, medicinal chemistry, materials science, and biomedical applications. However, conventional approaches to arylboronic acids often rely on transition-metal catalysts, prefunctionalized organometallic reagents, or strongly basic conditions, which may limit functional-group tolerance and raise concerns related to cost, metal residues, and environmental sustainability. Herein, we report a visible-light-induced, transition-metal-free and strong-base-free borylation of arylsulfonium salts with tetrahydroxydiboron for the direct preparation of arylboronic acids. This protocol proceeds under mild conditions at room temperature without an external photocatalyst or strong base, highlighting its operational simplicity and green-chemistry potential. A broad range of arylsulfonium salts, including halogenated arenes, biphenyl derivatives, aryl ethers, ester-containing substrates, and drug-derived molecules, are efficiently converted into the corresponding arylboronic acids. Preliminary mechanistic studies are consistent with the possible involvement of substrate interactions and radical species under light irradiation. The combination of visible-light activation, catalyst-free conditions, and broad functional-group compatibility makes this method an attractive platform for sustainable arylboronic acid synthesis and late-stage molecular diversification.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"382 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aman Singh,Divya Singh,Pooja Kumari,Ankur Yadav,Prince Kumar,Sundaram Singh
Recently, catalytic electron donor–acceptor (EDA) complexes have emerged as an effective and environmentally friendly alternative to metal-based (e.g., Ir and Ru) photoredox synthesis techniques. However, these complexes remain largely undiscovered and depend on properly designed acceptors that must be introduced beforehand. Here, we describe a novel EDA complex that utilises readily and inexpensively synthesised diazonium tetrafluoroborates as a catalytic acceptor for secondary amine arylation. The resulting EDA complex exhibits high functional-group tolerance and a broad substrate scope, encompassing over 40 substrates in C(sp2)–N bond-forming processes. The procedure features mild conditions, a green solvent, and minimal energy input, with excellent tolerance to functional groups.
{"title":"Visible light-induced C(sp)–N bond formation from diazonium tetrafluoroborates and secondary amines electron donor–acceptor complex formation","authors":"Aman Singh,Divya Singh,Pooja Kumari,Ankur Yadav,Prince Kumar,Sundaram Singh","doi":"10.1039/d6qo00858e","DOIUrl":"https://doi.org/10.1039/d6qo00858e","url":null,"abstract":"Recently, catalytic electron donor–acceptor (EDA) complexes have emerged as an effective and environmentally friendly alternative to metal-based (e.g., Ir and Ru) photoredox synthesis techniques. However, these complexes remain largely undiscovered and depend on properly designed acceptors that must be introduced beforehand. Here, we describe a novel EDA complex that utilises readily and inexpensively synthesised diazonium tetrafluoroborates as a catalytic acceptor for secondary amine arylation. The resulting EDA complex exhibits high functional-group tolerance and a broad substrate scope, encompassing over 40 substrates in C(sp2)–N bond-forming processes. The procedure features mild conditions, a green solvent, and minimal energy input, with excellent tolerance to functional groups.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973557","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Min Zhang,Shun Zhou,You-Ping Tian,Rui-Rui Li,Xiong-Li Liu,Ying Zhou,Xiong-Wei Liu
An organocatalytic asymmetric dearomative [3 + 2] cycloaddition between 2-nitrobenzofurans and 2-(N-2,2,2-trifluoroethyl) benzo[b]thiophene-2,3-dione-derived ketimines is described for the first time. A broad range of optically pure spiro hydrobenzofuranpyrrolidine–benzothiophenes bearing four contiguous stereocenters, including a spiro-quaternary carbon stereocenter, were obtained in high yields with excellent stereocontrol (up to 96% yield, >20 : 1 dr in all cases, and up to 99% ee). The synthetic utility of this method is demonstrated through a scale-up experiment and successful late-stage functionalization of complex bioactive molecules. Preliminary biological activity evaluations highlight the potential of this spirocyclic scaffold for medicinal chemistry exploration.
{"title":"Enantioselective dearomative [3 + 2] cycloaddition to access chiral spiro hydrobenzofuranpyrrolidine–benzothiophenes","authors":"Min Zhang,Shun Zhou,You-Ping Tian,Rui-Rui Li,Xiong-Li Liu,Ying Zhou,Xiong-Wei Liu","doi":"10.1039/d6qo00814c","DOIUrl":"https://doi.org/10.1039/d6qo00814c","url":null,"abstract":"An organocatalytic asymmetric dearomative [3 + 2] cycloaddition between 2-nitrobenzofurans and 2-(N-2,2,2-trifluoroethyl) benzo[b]thiophene-2,3-dione-derived ketimines is described for the first time. A broad range of optically pure spiro hydrobenzofuranpyrrolidine–benzothiophenes bearing four contiguous stereocenters, including a spiro-quaternary carbon stereocenter, were obtained in high yields with excellent stereocontrol (up to 96% yield, >20 : 1 dr in all cases, and up to 99% ee). The synthetic utility of this method is demonstrated through a scale-up experiment and successful late-stage functionalization of complex bioactive molecules. Preliminary biological activity evaluations highlight the potential of this spirocyclic scaffold for medicinal chemistry exploration.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A divergent annulation reaction of α-phosphoryl diazoalkanes with 3-iminoindolin-2-ones is developed for the facile construction of diastereospecific spiro indolinone-phosphinolactams. Precise control over [2 + 2] and [4 + 2] annuloselectivity is achieved by tuning reaction conditions, delivering the corresponding diastereospecific spiro β- and δ-phosphinolactam-indolinones, respectively. This work realizes the first successful synthesis of spirocyclic β-phosphinolactams and the first synthetic strategy to incorporate phosphinolactam motifs into the spiro indolinone scaffold. The unprecedented thermal transformation from β-phosphinolactams to δ-phosphinolactams is realized, and a plausible reaction mechanism is proposed and verified via DFT calculations. Molecular docking studies targeting MDM2 reveal that both classes of spiro-phosphinolactam-indolinones exhibit remarkable broad-spectrum anticancer potential as promising lead compounds.
{"title":"Divergent diastereospecific synthesis of spiro β- and δ-phosphinolactam-indolinones with tunable annuloselectivity","authors":"Yuliang Wei,Jiameng Yu,Chengzhuo Wang,Jiaxi Xu","doi":"10.1039/d6qo00750c","DOIUrl":"https://doi.org/10.1039/d6qo00750c","url":null,"abstract":"A divergent annulation reaction of α-phosphoryl diazoalkanes with 3-iminoindolin-2-ones is developed for the facile construction of diastereospecific spiro indolinone-phosphinolactams. Precise control over [2 + 2] and [4 + 2] annuloselectivity is achieved by tuning reaction conditions, delivering the corresponding diastereospecific spiro β- and δ-phosphinolactam-indolinones, respectively. This work realizes the first successful synthesis of spirocyclic β-phosphinolactams and the first synthetic strategy to incorporate phosphinolactam motifs into the spiro indolinone scaffold. The unprecedented thermal transformation from β-phosphinolactams to δ-phosphinolactams is realized, and a plausible reaction mechanism is proposed and verified via DFT calculations. Molecular docking studies targeting MDM2 reveal that both classes of spiro-phosphinolactam-indolinones exhibit remarkable broad-spectrum anticancer potential as promising lead compounds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The field of asymmetric photochemistry has emerged as a promising and powerful platform for a wide range of significant organic transformations, many of which are difficult to accomplish via traditional methods. However, the pursuit of enantioselectivity in photochemical reactions under mild conditions remains a formidable challenge, largely due to the high reactivity of open-shell species. In recent years, remarkable progress has been achieved by combining visible light with various catalytic strategies, including organic, transition-metal, Lewis, anion-bonding, and enzyme catalysis. This review summarises recent developments in visible-light-mediated enantioselective organocatalysed strategies since 2020. Particular emphasis is placed on providing an overview of the mechanisms of asymmetric induction in photochemical processes. We hope that this perspective will help readers understand how to control the reactivity of radical species and will inspire the development of novel enantioselective reaction modes.
{"title":"(Photo)organocatalytic options for metal-free visible-light-mediated asymmetric reactions","authors":"Jiaxu Feng,Luca Nicchio,Siqi Li,Lulu Xu,Kui Lu,Xia Zhao,Stefano Protti","doi":"10.1039/d6qo00887a","DOIUrl":"https://doi.org/10.1039/d6qo00887a","url":null,"abstract":"The field of asymmetric photochemistry has emerged as a promising and powerful platform for a wide range of significant organic transformations, many of which are difficult to accomplish via traditional methods. However, the pursuit of enantioselectivity in photochemical reactions under mild conditions remains a formidable challenge, largely due to the high reactivity of open-shell species. In recent years, remarkable progress has been achieved by combining visible light with various catalytic strategies, including organic, transition-metal, Lewis, anion-bonding, and enzyme catalysis. This review summarises recent developments in visible-light-mediated enantioselective organocatalysed strategies since 2020. Particular emphasis is placed on providing an overview of the mechanisms of asymmetric induction in photochemical processes. We hope that this perspective will help readers understand how to control the reactivity of radical species and will inspire the development of novel enantioselective reaction modes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"59 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammad Taghi Nazeri,Tahereh Nasiriani,Marzieh Norouzi,Saeed Torabi,Mohammad Amin Vakili,Ahmad Shaabani
Isocyanide-based multicomponent reactions (I-MCRs) are among the most important synthetic methods for producing a wide range of commercial drugs, natural product analogues, pseudopeptides, and biologically active compounds. Their versatility and efficiency have attracted significant interest from organic chemists. The isocyanide functional group is one of the most unique and intriguing structures in organic chemistry due to its ability to act as a nucleophile, electrophile, carbene, radical acceptor, and metal ligand. The multifunctional and chameleonic properties of isocyanides enable them to engage in a diverse array of reactions, generating complex intermediates and unexpected products. Isocyanide displays remarkable reactivity and versatility, particularly in one-pot multicomponent reactions (MCRs) where it interacts with various reactive reagents, often yielding complex and unpredictable outcomes. Factors such as temperature, solvents, and catalysts play a critical role in these reactions, enhancing the unique reactivity of isocyanides and influencing the formation of unexpected products. This review explores the remarkable phenomena associated with I-MCRs, particularly their ability to yield unexpected products. To gain deeper insight, we thoroughly examine both the predicted and unanticipated reaction outcomes, along with the underlying mechanisms. Additionally, we discuss the key factors influencing these unexpected pathways. We believe that a detailed evaluation of these reactions can provide valuable guidance for the selection and design of future MCR systems in various applications.
{"title":"Unexpected products in isocyanide-based multicomponent reactions","authors":"Mohammad Taghi Nazeri,Tahereh Nasiriani,Marzieh Norouzi,Saeed Torabi,Mohammad Amin Vakili,Ahmad Shaabani","doi":"10.1039/d6qo00608f","DOIUrl":"https://doi.org/10.1039/d6qo00608f","url":null,"abstract":"Isocyanide-based multicomponent reactions (I-MCRs) are among the most important synthetic methods for producing a wide range of commercial drugs, natural product analogues, pseudopeptides, and biologically active compounds. Their versatility and efficiency have attracted significant interest from organic chemists. The isocyanide functional group is one of the most unique and intriguing structures in organic chemistry due to its ability to act as a nucleophile, electrophile, carbene, radical acceptor, and metal ligand. The multifunctional and chameleonic properties of isocyanides enable them to engage in a diverse array of reactions, generating complex intermediates and unexpected products. Isocyanide displays remarkable reactivity and versatility, particularly in one-pot multicomponent reactions (MCRs) where it interacts with various reactive reagents, often yielding complex and unpredictable outcomes. Factors such as temperature, solvents, and catalysts play a critical role in these reactions, enhancing the unique reactivity of isocyanides and influencing the formation of unexpected products. This review explores the remarkable phenomena associated with I-MCRs, particularly their ability to yield unexpected products. To gain deeper insight, we thoroughly examine both the predicted and unanticipated reaction outcomes, along with the underlying mechanisms. Additionally, we discuss the key factors influencing these unexpected pathways. We believe that a detailed evaluation of these reactions can provide valuable guidance for the selection and design of future MCR systems in various applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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