Peptide stapling has emerged as a valuable approach for modulating peptide structures and enhancing their functional properties, with broad applications for drug discovery and biomolecular engineering. Among the diverse stapling strategies, polyfluorinated reagent-mediated approaches stand out due to their unique ability to provide desirable physicochemical properties such as improved stability, lipophilicity, and binding affinity. This review highlights recent advancements in polyfluorinated reagents for native peptide stapling, focusing on three major classes: arylation, vinylation, and amidation reagents. These reagents enable precise peptide modifications by leveraging the reactivity and selectivity modulated by fluorine substituents, facilitating the engineering of native peptides and biologics.
{"title":"Polyfluorinated Reagents for Peptide Stapling","authors":"Wanzhen Lin, Xin Ding, Junwei Han, Lishuang Yu, Fa-Jie Chen","doi":"10.1039/d5qo00112a","DOIUrl":"https://doi.org/10.1039/d5qo00112a","url":null,"abstract":"Peptide stapling has emerged as a valuable approach for modulating peptide structures and enhancing their functional properties, with broad applications for drug discovery and biomolecular engineering. Among the diverse stapling strategies, polyfluorinated reagent-mediated approaches stand out due to their unique ability to provide desirable physicochemical properties such as improved stability, lipophilicity, and binding affinity. This review highlights recent advancements in polyfluorinated reagents for native peptide stapling, focusing on three major classes: arylation, vinylation, and amidation reagents. These reagents enable precise peptide modifications by leveraging the reactivity and selectivity modulated by fluorine substituents, facilitating the engineering of native peptides and biologics.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"208 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385509","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}
Huilan Zhang, Michael Ho-Yeung Chan, Jonathan Lam, Ming-Yi Leung, Lixin Wu, Vivian Wing-Wah Yam
A new class of water-soluble amphiphilic Schiff base-containing platinum(II) complexes with dendritic triethylene glycol units has been investigated to show self-assembly properties by the balance of multiple noncovalent interactions including hydrophobic, intermolecular Pt⋯Pt and π–π stacking interactions in water or DMSO–water solutions, accompanied by drastic spectroscopic changes. The UV–vis spectra have been recorded, and the electronic structures and intermolecular Pt⋯Pt interactions have been confirmed by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. These complexes have been found to exhibit a cooperative self-assembly mechanism, in which the molecules were stacked in a head-to-tail arrangement in a slightly staggered fashion. Additionally, the length of the alkoxy chains has been found to show a significant effect on the extent of Pt⋯Pt and π–π stacking interactions and the stability of their self-assembled aggregates. Under the influence of temperature, this class of Schiff base-containing platinum(II) complexes has been shown to exhibit an unexpected hysteresis effect and unusual thermo-responsive behavior accompanied by morphological transformation. This work represents a rare example of a systematic study on the self-assembly properties of water-soluble platinum(II) Schiff base complexes induced by molecular hydrophobicity, solvation and temperature. It provides an in-depth insight into the rational molecular design for the construction of supramolecular architectures and potential advances in stimuli-responsive probes.
{"title":"Solvation and temperature-modulated supramolecular assembly of amphiphilic water-soluble Schiff base-containing platinum(II) complexes","authors":"Huilan Zhang, Michael Ho-Yeung Chan, Jonathan Lam, Ming-Yi Leung, Lixin Wu, Vivian Wing-Wah Yam","doi":"10.1039/d4qo02258k","DOIUrl":"https://doi.org/10.1039/d4qo02258k","url":null,"abstract":"A new class of water-soluble amphiphilic Schiff base-containing platinum(<small>II</small>) complexes with dendritic triethylene glycol units has been investigated to show self-assembly properties by the balance of multiple noncovalent interactions including hydrophobic, intermolecular Pt⋯Pt and π–π stacking interactions in water or DMSO–water solutions, accompanied by drastic spectroscopic changes. The UV–vis spectra have been recorded, and the electronic structures and intermolecular Pt⋯Pt interactions have been confirmed by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. These complexes have been found to exhibit a cooperative self-assembly mechanism, in which the molecules were stacked in a head-to-tail arrangement in a slightly staggered fashion. Additionally, the length of the alkoxy chains has been found to show a significant effect on the extent of Pt⋯Pt and π–π stacking interactions and the stability of their self-assembled aggregates. Under the influence of temperature, this class of Schiff base-containing platinum(<small>II</small>) complexes has been shown to exhibit an unexpected hysteresis effect and unusual thermo-responsive behavior accompanied by morphological transformation. This work represents a rare example of a systematic study on the self-assembly properties of water-soluble platinum(<small>II</small>) Schiff base complexes induced by molecular hydrophobicity, solvation and temperature. It provides an in-depth insight into the rational molecular design for the construction of supramolecular architectures and potential advances in stimuli-responsive probes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385458","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}
Direct incorporation of deuterauted functionalizties into molecules has emerged as an attractive approch in organic synthesis. Among them, the deuterauted selenomethyl is of great interest bue still less explored due to the lack of versatile synthons. Here, an electrophilic trideuteromethylselenating reagent, S-Methyl-d3 benzenesulfonoselenoate with >99% D-incorporation has been developed, which can be facilely prepared in one step and enable trideuteromethylselenation for a wide range of nucleophiles or electrophiles including boronic acids, boronic acids esters, terminal alkynes, -ketoesters, oxindoles and diazodium salts under mild reaction conditions. Moreover, difunctionalization of unactivated of alkenes by simultaneously construction of C-S and C-SeCD3 bonds are well-documented. The utility of odourless electrophilic SeCD3 reagent has been highlighted by late-stage modification of bioactive molecules with high efficiency.
{"title":"Direct Trideuteromethylselenation with a Shelf-Stable Reagent Se-Methyl-d3 Selenosulfonate","authors":"Guofang Guo, Yan Zhang, Ziting Huang, Wen Liu, Xueyi Lu, Zihan Liu, Xu-Qiong Xiao, Ying Bai, Xinxin Shao","doi":"10.1039/d4qo02396j","DOIUrl":"https://doi.org/10.1039/d4qo02396j","url":null,"abstract":"Direct incorporation of deuterauted functionalizties into molecules has emerged as an attractive approch in organic synthesis. Among them, the deuterauted selenomethyl is of great interest bue still less explored due to the lack of versatile synthons. Here, an electrophilic trideuteromethylselenating reagent, S-Methyl-d3 benzenesulfonoselenoate with >99% D-incorporation has been developed, which can be facilely prepared in one step and enable trideuteromethylselenation for a wide range of nucleophiles or electrophiles including boronic acids, boronic acids esters, terminal alkynes, -ketoesters, oxindoles and diazodium salts under mild reaction conditions. Moreover, difunctionalization of unactivated of alkenes by simultaneously construction of C-S and C-SeCD3 bonds are well-documented. The utility of odourless electrophilic SeCD3 reagent has been highlighted by late-stage modification of bioactive molecules with high efficiency.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385508","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}
Artificial intelligence (AI) is transforming molecular catalysis by addressing long-standing challenges in retrosynthetic design, catalyst design, reaction prediction, and autonomous experimentation. AI-powered tools enable chemists to explore high-dimensional chemical spaces, optimize reaction conditions, and accelerate novel reaction discovery with unparalleled efficiency and precision. These innovations are reshaping traditional workflows, transitioning from expert-driven, labor-intensive methodologies to intelligence-guided, data-driven processes. Despite these transformative achievements, significant challenges persist. Critical issues include the demand for high-quality, reliable datasets, the seamless integration of domain-specific chemical knowledge into AI models, and the discrepancy between model predictions and experimental validation. Addressing these barriers is essential to fully unlock AI's potential in molecular catalysis. This review explores recent advancements, enduring challenges, and emerging opportunities in AI-driven molecular catalysis. By focusing on real-world applications and highlighting representative studies, it aims to provide a clear and forward-looking perspective on how AI is redefining the field and paving the way for the next generation of chemical discovery.
{"title":"AI Molecular Catalysis: Where Are We Now?","authors":"Zhenzhi Tan, Qi Yang, Sanzhong Luo","doi":"10.1039/d4qo02363c","DOIUrl":"https://doi.org/10.1039/d4qo02363c","url":null,"abstract":"Artificial intelligence (AI) is transforming molecular catalysis by addressing long-standing challenges in retrosynthetic design, catalyst design, reaction prediction, and autonomous experimentation. AI-powered tools enable chemists to explore high-dimensional chemical spaces, optimize reaction conditions, and accelerate novel reaction discovery with unparalleled efficiency and precision. These innovations are reshaping traditional workflows, transitioning from expert-driven, labor-intensive methodologies to intelligence-guided, data-driven processes. Despite these transformative achievements, significant challenges persist. Critical issues include the demand for high-quality, reliable datasets, the seamless integration of domain-specific chemical knowledge into AI models, and the discrepancy between model predictions and experimental validation. Addressing these barriers is essential to fully unlock AI's potential in molecular catalysis. This review explores recent advancements, enduring challenges, and emerging opportunities in AI-driven molecular catalysis. By focusing on real-world applications and highlighting representative studies, it aims to provide a clear and forward-looking perspective on how AI is redefining the field and paving the way for the next generation of chemical discovery.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385510","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 a self-photocatalysis-enabled divergent synthesis of benzo[b]fluorenones and benzo[b]fluorenols from enone-ynes in batch and flow under mild and metal-, photocatalyst- and redox-agent-free conditions. The photocatalytic system exhibits multiple activities, including energy, electron and hydrogen atom transfers as well as photocycloaddition. Under blue-light irradiation, benzo[b]fluorenones were synthesized through an oxidative mechanism involving superoxide radical and singlet oxygen as key hydrogen-atom transfer intermediates. Alternatively, benzo[b]fluorenols were obtained via a redox-neutral pathway under violet-light irradiation, utilizing quinuclidine as a hydrogen atom transfer catalyst. The scalability, flow adaptability as well as sunlight experiments highlight the practical potential.
{"title":"Self-photocatalysis with multiple activities: divergent synthesis of benzo[b]fluorenones and benzo[b]fluorenols from enone-ynes","authors":"Jifu Shi, Qingyao Sun, YunLing Gao, Yongqin Hu, Weili Li, Binbin He, Shulin Gao, Shaoguang Sun, Deqiang Liang","doi":"10.1039/d4qo02444c","DOIUrl":"https://doi.org/10.1039/d4qo02444c","url":null,"abstract":"Herein, we report a self-photocatalysis-enabled divergent synthesis of benzo[b]fluorenones and benzo[b]fluorenols from enone-ynes in batch and flow under mild and metal-, photocatalyst- and redox-agent-free conditions. The photocatalytic system exhibits multiple activities, including energy, electron and hydrogen atom transfers as well as photocycloaddition. Under blue-light irradiation, benzo[b]fluorenones were synthesized through an oxidative mechanism involving superoxide radical and singlet oxygen as key hydrogen-atom transfer intermediates. Alternatively, benzo[b]fluorenols were obtained via a redox-neutral pathway under violet-light irradiation, utilizing quinuclidine as a hydrogen atom transfer catalyst. The scalability, flow adaptability as well as sunlight experiments highlight the practical potential.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"86 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385456","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}
Feifei Jin, Cangzhu Hu, Shuaijie Wu, Guodong Zhang, Ying Han, Chao-Guo Yan, Wenbo Li, Chaoshen Zhang, Lei Wang
A highly efficient Pd-catalyzed enantioselective carboetherification reaction of β,γ-unsaturated ketoximes with propargylic acetates is demonstrated. This method provides various chiral isoxazolines bearing multisubstituted allene groups in good yields with excellent enantioselectivities. The sterically electron-rich BINOL-derived phosphoramidite ligand exhibits highly efficient control over both chemoselectivity and enantioselectivity. The salient features of this reaction include readily available starting materials, broad functional group tolerance, an easy scale-up, versatile transformations and promising photo-physical properties. DFT calculations were carried out to disclose the detailed mechanism and origins of the enantioselectivity.
{"title":"Enantioselective synthesis of isoxazolines bearing allenes by palladium-catalyzed carboetherification of β,γ-unsaturated ketoximes with propargylic acetates","authors":"Feifei Jin, Cangzhu Hu, Shuaijie Wu, Guodong Zhang, Ying Han, Chao-Guo Yan, Wenbo Li, Chaoshen Zhang, Lei Wang","doi":"10.1039/d4qo02319f","DOIUrl":"https://doi.org/10.1039/d4qo02319f","url":null,"abstract":"A highly efficient Pd-catalyzed enantioselective carboetherification reaction of β,γ-unsaturated ketoximes with propargylic acetates is demonstrated. This method provides various chiral isoxazolines bearing multisubstituted allene groups in good yields with excellent enantioselectivities. The sterically electron-rich BINOL-derived phosphoramidite ligand exhibits highly efficient control over both chemoselectivity and enantioselectivity. The salient features of this reaction include readily available starting materials, broad functional group tolerance, an easy scale-up, versatile transformations and promising photo-physical properties. DFT calculations were carried out to disclose the detailed mechanism and origins of the enantioselectivity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385507","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}
Wen-Huan Tang, Li-Yuan Wu, Quan-Quan Zhou, Jie-Ping Wan
Ynones are essential scaffolds for a diverse array of active molecules, and also serve as important synthetic intermediates. Herein, we describe a visible light-induced photoredox strategy for the synthesis of ynones using carboxylic acids and alkynyl sulfones. The synthesis protocol features mild reaction conditions, and moderate tolerance with respect to functional groups. Mechanistic studies have demonstrated that the deoxygenative ynonylation proceeds via acyl radical formation, followed by the capture of an alkynylation reagent to generate internal ynones with the loss of a sulfonyl radical. The synthetic utility of this methodology is demonstrated by the utilization of synthesized ynones in the preparation of commercially important heterocycles.
{"title":"Photoredox catalytic phosphine-mediated deoxygenative alkynylation of carboxylic acids with alkynyl sulfones for alkynone synthesis","authors":"Wen-Huan Tang, Li-Yuan Wu, Quan-Quan Zhou, Jie-Ping Wan","doi":"10.1039/d4qo02109f","DOIUrl":"https://doi.org/10.1039/d4qo02109f","url":null,"abstract":"Ynones are essential scaffolds for a diverse array of active molecules, and also serve as important synthetic intermediates. Herein, we describe a visible light-induced photoredox strategy for the synthesis of ynones using carboxylic acids and alkynyl sulfones. The synthesis protocol features mild reaction conditions, and moderate tolerance with respect to functional groups. Mechanistic studies have demonstrated that the deoxygenative ynonylation proceeds via acyl radical formation, followed by the capture of an alkynylation reagent to generate internal ynones with the loss of a sulfonyl radical. The synthetic utility of this methodology is demonstrated by the utilization of synthesized ynones in the preparation of commercially important heterocycles.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375521","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 strategic design and development of organo-catalysts for the efficient and stereoselective synthesis of O-aryl glycosides, an otherwise challenging task in carbohydrate chemistry, remains crucial. Non-covalent interactions (NCIs) based catalysts are emerging as essential synthetic tools for achieving defined anomeric selectivity in glycosylation reactions. However, their use has been predominantly explored for the synthesis of O- and C-glycosides. In this work, we present a highly efficient, robust and practical catalytic strategy for the diastereoselective (α:β > 30:1) synthesis of intriguing O-aryl glycosides using simple, easily accessible, cost-effective and strain-free unsubstituted pyridinium tetrafluoroborate salt as a catalyst at ambient conditions via activation of glycosylimidate donors through non-covalent hydrogen bonding interactions (NCIs). Detailed mechanistic investigations have uncovered a pivotal role of the designed catalyst in diastereoselective O-aryl glycosylations. The catalyst not only activates glycosylimidate donors but also enhances the nucleophilicity of phenols through dual hydrogen bonding and facial selectivity in the reaction is controlled by π-π interactions of the aromatic system. The effectiveness of the present method is further demonstrated through its broad substrate scope with respect to donors and acceptors and its applicability in gram-scale synthesis, allowing for diversification of the phenol moiety.
{"title":"Exploiting π and Hydrogen Bonding Interactions of Strain-free Pyridinium Tetrafluoroborate Salt for Stereoselective Synthesis of O-Aryl Glycosides","authors":"Anjali Aghi, Sankar Sau, Amit Kumar","doi":"10.1039/d4qo02401j","DOIUrl":"https://doi.org/10.1039/d4qo02401j","url":null,"abstract":"The strategic design and development of organo-catalysts for the efficient and stereoselective synthesis of O-aryl glycosides, an otherwise challenging task in carbohydrate chemistry, remains crucial. Non-covalent interactions (NCIs) based catalysts are emerging as essential synthetic tools for achieving defined anomeric selectivity in glycosylation reactions. However, their use has been predominantly explored for the synthesis of O- and C-glycosides. In this work, we present a highly efficient, robust and practical catalytic strategy for the diastereoselective (α:β > 30:1) synthesis of intriguing O-aryl glycosides using simple, easily accessible, cost-effective and strain-free unsubstituted pyridinium tetrafluoroborate salt as a catalyst at ambient conditions via activation of glycosylimidate donors through non-covalent hydrogen bonding interactions (NCIs). Detailed mechanistic investigations have uncovered a pivotal role of the designed catalyst in diastereoselective O-aryl glycosylations. The catalyst not only activates glycosylimidate donors but also enhances the nucleophilicity of phenols through dual hydrogen bonding and facial selectivity in the reaction is controlled by π-π interactions of the aromatic system. The effectiveness of the present method is further demonstrated through its broad substrate scope with respect to donors and acceptors and its applicability in gram-scale synthesis, allowing for diversification of the phenol moiety.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375488","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}
Electrocyclic reactions represent a fundamental class of organic transformations that play a pivotal role in the synthesis of structurally intricate and biologically active natural products. These reactions adhere to the Woodward−Hoffmann rules, which elucidate the stereochemical outcomes based on the symmetry properties of the molecular orbitals involved. Characterized by their ability to dictate regio- and stereochemistry with high fidelity, electrocyclic reactions have proven to be a reliable and efficient method for assembling complex polycyclic frameworks. This review highlights recent advances in the application of electrocyclic reactions within the total synthesis of notable natural products. It also includes short sections on electrocyclic reactions in biosynthesis and key methodological developments in this area over recent years, aiming to complement existing reviews.
{"title":"Recent Advances on Electrocyclic Reactions in Complex Natural Product Synthesis: An Update","authors":"Ruyi Chen, Yanlin Liu, Hanfeng Ding","doi":"10.1039/d4qo02276a","DOIUrl":"https://doi.org/10.1039/d4qo02276a","url":null,"abstract":"Electrocyclic reactions represent a fundamental class of organic transformations that play a pivotal role in the synthesis of structurally intricate and biologically active natural products. These reactions adhere to the Woodward−Hoffmann rules, which elucidate the stereochemical outcomes based on the symmetry properties of the molecular orbitals involved. Characterized by their ability to dictate regio- and stereochemistry with high fidelity, electrocyclic reactions have proven to be a reliable and efficient method for assembling complex polycyclic frameworks. This review highlights recent advances in the application of electrocyclic reactions within the total synthesis of notable natural products. It also includes short sections on electrocyclic reactions in biosynthesis and key methodological developments in this area over recent years, aiming to complement existing reviews.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"84 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143367456","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}
In this study, an efficient method for one-pot synthesis of carbazoles from readily available nitroarenes and Grignard reagents by intermolecular thermal C-N bond coupling followed by a photoinduced aza-6π electrocyclization reaction is reported. The photochemical pathway only requires irradiation of the reaction mixture with purple light (390-395 nm), without any external catalysts and additives, thus providing a novel and step-economic route for the synthesis of carbazoles. Mechanistic studies suggest that nitrosoarene and diarylamine are important intermediates in the reaction process.
{"title":"Synthesis of Carbazoles: Light-Promoted Tandem Coupling of Nitroarenes with Grignard Reagents","authors":"Chen Yang, Ya-Fei Wan, Tong Sun, Gang Li, Zhang-Jie Shi, Dong Xue","doi":"10.1039/d5qo00019j","DOIUrl":"https://doi.org/10.1039/d5qo00019j","url":null,"abstract":"In this study, an efficient method for one-pot synthesis of carbazoles from readily available nitroarenes and Grignard reagents by intermolecular thermal C-N bond coupling followed by a photoinduced aza-6π electrocyclization reaction is reported. The photochemical pathway only requires irradiation of the reaction mixture with purple light (390-395 nm), without any external catalysts and additives, thus providing a novel and step-economic route for the synthesis of carbazoles. Mechanistic studies suggest that nitrosoarene and diarylamine are important intermediates in the reaction process.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192390","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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