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Organic Chemistry Frontiers Outstanding Paper Awards 2014–2023 2014-2023 年有机化学前沿杰出论文奖
IF 4.6 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-14 DOI: 10.1039/D5QO90009C

A graphical abstract is available for this content

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引用次数: 0
Photochemical generation of heteroatom (N, Si, B) or carbon radicals leveraging preinstalled carboxylic acids 利用预装羧酸,光化学生成杂原子(N、Si、B)或碳自由基
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-12 DOI: 10.1039/d5qo00036j
Chao Tian, Lei Shi
In the domain of organic chemistry, radicals derived from elements such as nitrogen, silicon, boron, and carbon have long played an indispensable role as pivotal intermediates in numerous transformations. Consequently, the development of novel methods for the efficient generation of these radicals received widespread attention. The use of “preinstalled carboxyl groups” as activating moieties for generating the corresponding radicals provided milder conditions, faster reactions, and exceptional functional group compatibility. Radicals formed from the decarboxylation steps not only participated in single photocatalytic transformations but also enabled dual catalytic cross-coupling reactions by integrating photocatalysis with other catalytic processes. This review provided an overview of recent advancements in generating N, Si, B, and C radicals through the decarboxylation of preinstalled carboxyl substrates under visible light catalysis.
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引用次数: 0
Recent advances in hydrofunctionalisation of cyclopropenes via carbon–heteroatom bond formation
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-12 DOI: 10.1039/d4qo02441a
Jorge García-Lacuna, Gema Domínguez, Ángel Manu Martínez, Javier Pérez-Castells
Hydrofunctionalisation of cyclopropenes represents a redox-neutral and atom-economic strategy to obtain polyfunctionalised cyclopropanes. The extraordinary potential of heteroatom-containing cyclopropanes in organic and medicinal chemistry has driven a growing interest in developing new methodologies for the selective addition of hydrogen–heteroatom bonds across the carbon–carbon double bond of cyclopropenes. Despite the apparent simplicity of these transformations, they involve significant challenges in terms of stereoselectivity. Continuous efforts to control the regio-, diastereo- and enantioselectivity of these processes, especially by applying different transition metal catalysts, have led to numerous reports. This review comprehensively examines the developments and advances in the selective hydrofunctionalisation of cyclopropenes by carbon–heteroatom bond formation.
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引用次数: 0
Polyfluorinated Reagents for Peptide Stapling
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-11 DOI: 10.1039/d5qo00112a
Wanzhen Lin, Xin Ding, Junwei Han, Lishuang Yu, Fa-Jie Chen
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}
引用次数: 0
Solvation and temperature-modulated supramolecular assembly of amphiphilic water-soluble Schiff base-containing platinum(II) complexes
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-11 DOI: 10.1039/d4qo02258k
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}
引用次数: 0
Direct Trideuteromethylselenation with a Shelf-Stable Reagent Se-Methyl-d3 Selenosulfonate
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-11 DOI: 10.1039/d4qo02396j
Guofang Guo, Yan Zhang, Ziting Huang, Wen Liu, Xueyi Lu, Zihan Liu, Xu-Qiong Xiao, Ying Bai, Xinxin Shao
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 &gt;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}
引用次数: 0
AI Molecular Catalysis: Where Are We Now?
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-11 DOI: 10.1039/d4qo02363c
Zhenzhi Tan, Qi Yang, Sanzhong Luo
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}
引用次数: 0
Self-photocatalysis with multiple activities: divergent synthesis of benzo[b]fluorenones and benzo[b]fluorenols from enone-ynes
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-11 DOI: 10.1039/d4qo02444c
Jifu Shi, Qingyao Sun, YunLing Gao, Yongqin Hu, Weili Li, Binbin He, Shulin Gao, Shaoguang Sun, Deqiang Liang
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}
引用次数: 0
Enantioselective synthesis of isoxazolines bearing allenes by palladium-catalyzed carboetherification of β,γ-unsaturated ketoximes with propargylic acetates
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-11 DOI: 10.1039/d4qo02319f
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}
引用次数: 0
Photoredox catalytic phosphine-mediated deoxygenative alkynylation of carboxylic acids with alkynyl sulfones for alkynone synthesis
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-10 DOI: 10.1039/d4qo02109f
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}
引用次数: 0
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Organic Chemistry Frontiers
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