Herein, using tricarbazole as the electron donor and four aromatic rings with varied electron cloud density as acceptor, four homologous donor-acceptor (D–A) architectures (TrCzDAa~d) were divergently synthesized and characterized. Their steady-state and transient photophysical properties were subsequently investigated, in which their intramolecular charge transfer transitions were disclosed by solvent-dependent fluorescence spectra. Interestingly, the electron-rich acceptor could result in the blue shift of fluorescence, while the electron-deficient acceptor led to red-shifted fluorescence emission.Furthermore, intense and stable electrochemiluminescence (ECL) signals were observed for all architectures. In contrast, the ECL intensity enhanced with the increasing electron cloud density of the acceptor. Finally, TrCzDAb displaying the optimal ECL performance, was used as the electrode modification material to construct an epinephrine sensor, which demonstrated high sensitivity, excellent stability, and remarkable selectivity. This work elucidated the regulatory role of electron cloud density of the acceptor on the optoelectronic properties of D–A architectures and provides new insights for developing novel high-performance optoelectronic materials and sensors.
{"title":"Tricarbazole-based donor–acceptor architectures with diverse acceptors: synthesis, properties and applications","authors":"Huabi Xie, Yu Zuo, Chengye Yuan, Peng Xu, Ningwen Sun, Hongxing Jia, Jinjin Ding, Qiang Huang, Jinling Zhang","doi":"10.1039/d5qo01633a","DOIUrl":"https://doi.org/10.1039/d5qo01633a","url":null,"abstract":"Herein, using tricarbazole as the electron donor and four aromatic rings with varied electron cloud density as acceptor, four homologous donor-acceptor (D–A) architectures (<strong>TrCzDAa~d</strong>) were divergently synthesized and characterized. Their steady-state and transient photophysical properties were subsequently investigated, in which their intramolecular charge transfer transitions were disclosed by solvent-dependent fluorescence spectra. Interestingly, the electron-rich acceptor could result in the blue shift of fluorescence, while the electron-deficient acceptor led to red-shifted fluorescence emission.Furthermore, intense and stable electrochemiluminescence (ECL) signals were observed for all architectures. In contrast, the ECL intensity enhanced with the increasing electron cloud density of the acceptor. Finally, <strong>TrCzDAb</strong> displaying the optimal ECL performance, was used as the electrode modification material to construct an epinephrine sensor, which demonstrated high sensitivity, excellent stability, and remarkable selectivity. This work elucidated the regulatory role of electron cloud density of the acceptor on the optoelectronic properties of D–A architectures and provides new insights for developing novel high-performance optoelectronic materials and sensors.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184559","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 hydroxylamines are important structural motifs and intermediates for a variety of drugs and bioactive molecules. Herein we report the first example of direct asymmetric reductive amination for the direct synthesis of N-H and N-alkyl chiral hydroxylamines. By utilizing complexes generated in situ from a neutral Ir(I) precursor and highly tunable CTPhos ligands as catalysts, we demonstrate that a selection of ketones can be reductively coupled with two types of hydroxylamine nitrogen sources to yield the corresponding chiral products in high yields and enantiomeric excesses, thereby eliminating the need to isolate and use (E)-isomers of oxime intermediates. The series of highly modulated and easily programmable CTPhos ligands promise a suitable enantio-environment for these reactions. Additionally, the chloride atom plays vital roles in the hydrogen addition step by forming a pair of hydrogen bonds among the catalytic species, hydroxylamine, and the protonated oxime intermediate. The H-bonding and other noncovalent interactions stabilize the key transition state and enable high enantioselectivity.
{"title":"Tunable CTPhos and Chloride Enabled Direct Asymmetric Reductive Amination for the Synthesis of Chial Hydroxylamines","authors":"Qishan Liu, Wenji Wang, Biying Liu, Haizhou Huang, Mingxin Chang","doi":"10.1039/d6qo00012f","DOIUrl":"https://doi.org/10.1039/d6qo00012f","url":null,"abstract":"Chiral hydroxylamines are important structural motifs and intermediates for a variety of drugs and bioactive molecules. Herein we report the first example of direct asymmetric reductive amination for the direct synthesis of N-H and N-alkyl chiral hydroxylamines. By utilizing complexes generated in situ from a neutral Ir(I) precursor and highly tunable CTPhos ligands as catalysts, we demonstrate that a selection of ketones can be reductively coupled with two types of hydroxylamine nitrogen sources to yield the corresponding chiral products in high yields and enantiomeric excesses, thereby eliminating the need to isolate and use (E)-isomers of oxime intermediates. The series of highly modulated and easily programmable CTPhos ligands promise a suitable enantio-environment for these reactions. Additionally, the chloride atom plays vital roles in the hydrogen addition step by forming a pair of hydrogen bonds among the catalytic species, hydroxylamine, and the protonated oxime intermediate. The H-bonding and other noncovalent interactions stabilize the key transition state and enable high enantioselectivity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"207 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146160909","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}
Shoucai Wang, Ziren Chen, Fei Xue, Yonghong Zhang, Bin Wang, Shaofeng Wu, Yu Xia, Weiwei Jin, Fanghua Ji, Chenjiang Liu
Direct C-H silylation of (thio)chromones was achieved by the combination of hydrogen atom transfer (HAT), photoredox and transition metal catalysis under ambient air conditions. High regioselectivity, oxidant-and noble metal-free conditions, and synergistic multiple catalysis were the major features of this protocol. Moreover, this approach can be safely conducted on a gram scale with hydrogen as the only byproduct.6
在环境空气条件下，通过氢原子转移（HAT）、光氧化还原（photoredox）和过渡金属催化（transition metal catalytic）的结合，实现了（thio）铬的直接C-H硅基化。高区域选择性、无氧化和无贵金属条件、协同多重催化是该工艺的主要特点。而且，这种方法可以安全地以克为单位进行，氢气是唯一的副产品
{"title":"Visible Light-Induced Regioselective/Dehydrogenative Silylation of (Thio)chromones via Tricatalytic Process","authors":"Shoucai Wang, Ziren Chen, Fei Xue, Yonghong Zhang, Bin Wang, Shaofeng Wu, Yu Xia, Weiwei Jin, Fanghua Ji, Chenjiang Liu","doi":"10.1039/d6qo00081a","DOIUrl":"https://doi.org/10.1039/d6qo00081a","url":null,"abstract":"Direct C-H silylation of (thio)chromones was achieved by the combination of hydrogen atom transfer (HAT), photoredox and transition metal catalysis under ambient air conditions. High regioselectivity, oxidant-and noble metal-free conditions, and synergistic multiple catalysis were the major features of this protocol. Moreover, this approach can be safely conducted on a gram scale with hydrogen as the only byproduct.6","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"157 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146160911","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}
Albert Artigas, Nicolas Vanthuyne, Jean-Valère Naubron, Denis Hagebaum-Reignier, Yannick Carissan, Maxime Remond, Ludovic Favereau, Harald Bock, Fabien Durola, Yoann Coquerel
The in-depth analysis of the configurational, (chir)optical and aromatic properties of two diastereomeric singly and triply twisted Möbius-shaped macrocycles, the cyclotris[5]helicenes, in which three [5]helicene fragments with like and unlike helicity are connected by three C(sp2)–C(sp2) single bonds, led to the conclusion that global π electronic delocalization exists in these molecules. This was analyzed as a consequence of the reduced torsion angle (≤ 30°) at the C(sp2)–C(sp2) single bonds connecting the [5]helicene fragments. The enantiomers of both diastereomeric cyclotris[5]helicenes were thoroughly analyzed experimentally by unpolarized and circularly polarized vibrational, absorption and luminescence (fluorescence and phosphorescence) precision spectroscopies, all correlated with advanced DFT models, which provided insightful data on their S0, S1 and T1 electronic states, and on their chirality. The theoretical analyses of aromaticity in both diastereomeric cyclotris[5]helicene macrocycles, as compared with recently reported analogues, confirmed their Möbius aromaticity.
{"title":"Electronic Properties of Diastereomeric Möbius Shaped Cyclotris[5]helicenes","authors":"Albert Artigas, Nicolas Vanthuyne, Jean-Valère Naubron, Denis Hagebaum-Reignier, Yannick Carissan, Maxime Remond, Ludovic Favereau, Harald Bock, Fabien Durola, Yoann Coquerel","doi":"10.1039/d5qo01741f","DOIUrl":"https://doi.org/10.1039/d5qo01741f","url":null,"abstract":"The in-depth analysis of the configurational, (chir)optical and aromatic properties of two diastereomeric singly and triply twisted Möbius-shaped macrocycles, the cyclotris[5]helicenes, in which three [5]helicene fragments with like and unlike helicity are connected by three C(sp<small><sup>2</sup></small>)–C(sp<small><sup>2</sup></small>) single bonds, led to the conclusion that global π electronic delocalization exists in these molecules. This was analyzed as a consequence of the reduced torsion angle (≤ 30°) at the C(sp<small><sup>2</sup></small>)–C(sp<small><sup>2</sup></small>) single bonds connecting the [5]helicene fragments. The enantiomers of both diastereomeric cyclotris[5]helicenes were thoroughly analyzed experimentally by unpolarized and circularly polarized vibrational, absorption and luminescence (fluorescence and phosphorescence) precision spectroscopies, all correlated with advanced DFT models, which provided insightful data on their S<small><sub>0</sub></small>, S<small><sub>1</sub></small> and T<small><sub>1</sub></small> electronic states, and on their chirality. The theoretical analyses of aromaticity in both diastereomeric cyclotris[5]helicene macrocycles, as compared with recently reported analogues, confirmed their Möbius aromaticity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"150 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146160910","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}
Zhan-Wei Fu, Chen-Yu Dou, Xiong Zhou, Feifei Fang, Mu-Peng Luo, Shu-Rong Ban, Shi Cao, Shou-Guo Wang
Axially chiral scaffolds are privileged motifs in natural products, bioactive agents, and asymmetric catalysis. Here, we present an enantioselective C–H arylation of 2-pyridones at the C6 position with diazo compounds, catalyzed by a chiral Rh(III) complex. This strategy enables direct, efficient, and modular construction of C–C axially chiral 2-pyridones with high yields and outstanding enantioselectivity (up to 99% yield, 99% ee). The method features a broad substrate scope, operational simplicity, and scalability, offering a versatile and practical route to diverse useful atropisomeric architectures.
{"title":"Rh(III)-Catalyzed Enantioselective C–H Arylation: Atroposelective Synthesis of 2-Pyridones from Diazo Compounds","authors":"Zhan-Wei Fu, Chen-Yu Dou, Xiong Zhou, Feifei Fang, Mu-Peng Luo, Shu-Rong Ban, Shi Cao, Shou-Guo Wang","doi":"10.1039/d5qo01764e","DOIUrl":"https://doi.org/10.1039/d5qo01764e","url":null,"abstract":"Axially chiral scaffolds are privileged motifs in natural products, bioactive agents, and asymmetric catalysis. Here, we present an enantioselective C–H arylation of 2-pyridones at the C6 position with diazo compounds, catalyzed by a chiral Rh(III) complex. This strategy enables direct, efficient, and modular construction of C–C axially chiral 2-pyridones with high yields and outstanding enantioselectivity (up to 99% yield, 99% ee). The method features a broad substrate scope, operational simplicity, and scalability, offering a versatile and practical route to diverse useful atropisomeric architectures.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139021","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}
Yue Wu, Kuirong Fu, Song Qin, Ming Ouyang, Zhiyao Yang, Yimin Cai, Wen Feng, Lihua Yuan, Xiaowei Li
Photoresponsive host macrocycles are attractive for their wide scope of applications in controlled molecular recognition, information storage, switchable catalysis, and smart materials. One of the challenges along this line lies in the construction of large size hosts with multiple photoactive groups, e.g. azobenzene, for light-controlled guest capture and release. Herein, we report a giant hydrogen-bonded aramide macrocycle incorporating four azobenzene units that enables light-controlled binding and release of cucurbit[5]uril (CB[5]). Single-crystal X-ray diffraction reveals that the tetra-azo-macrocycle adopts a relatively rigid figure of eight conformation constrained by intramolecular hydrogen bonding within the macrocyclic framework backbone. Photochemical studies demonstrate efficient photoisomerization from the thermally stable E,E,E,E-isomer to other isomeric states, reaching a maximum conversion of 95.7%. The amide oxygen-decorated cavity of the macrocycle selectively accommodates the smaller host CB[5] through multi-point hydrogen-bonding interactions, giving rise to forming a host-in-host complex. Most notably, light irradiation triggers the release of CB[5] in the presence of sodium cation, in sharp contrast to previously reported host-in-host systems in which guest release is typically difficult and relies solely on subtle host shape changes. This work demonstrates a rare example of exploiting a H-bonded aramide macrocycle with multiple azobenzene units for manoeuvring the uptake and release process in response to external photo-stimulus, and also implicates new possibilities for designing multi-state light-responsive materials.
{"title":"A photoswitchable tetra-azo macrocycle enabling light-controlled host-in-host binding and release of cucurbit[5]uril","authors":"Yue Wu, Kuirong Fu, Song Qin, Ming Ouyang, Zhiyao Yang, Yimin Cai, Wen Feng, Lihua Yuan, Xiaowei Li","doi":"10.1039/d5qo01751c","DOIUrl":"https://doi.org/10.1039/d5qo01751c","url":null,"abstract":"Photoresponsive host macrocycles are attractive for their wide scope of applications in controlled molecular recognition, information storage, switchable catalysis, and smart materials. One of the challenges along this line lies in the construction of large size hosts with multiple photoactive groups, e.g. azobenzene, for light-controlled guest capture and release. Herein, we report a giant hydrogen-bonded aramide macrocycle incorporating four azobenzene units that enables light-controlled binding and release of cucurbit[5]uril (CB[5]). Single-crystal X-ray diffraction reveals that the tetra-azo-macrocycle adopts a relatively rigid figure of eight conformation constrained by intramolecular hydrogen bonding within the macrocyclic framework backbone. Photochemical studies demonstrate efficient photoisomerization from the thermally stable <em>E</em>,<em>E</em>,<em>E</em>,<em>E</em>-isomer to other isomeric states, reaching a maximum conversion of 95.7%. The amide oxygen-decorated cavity of the macrocycle selectively accommodates the smaller host CB[5] through multi-point hydrogen-bonding interactions, giving rise to forming a <em>host-in-host</em> complex. Most notably, light irradiation triggers the release of CB[5] in the presence of sodium cation, in sharp contrast to previously reported <em>host-in-host</em> systems in which guest release is typically difficult and relies solely on subtle host shape changes. This work demonstrates a rare example of exploiting a H-bonded aramide macrocycle with multiple azobenzene units for manoeuvring the uptake and release process in response to external photo-stimulus, and also implicates new possibilities for designing multi-state light-responsive materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"295 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139020","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}
Yufan Yang, Dongxu Wang, Dongyang Jiang, Kaixuan Pan, Yingchen Wang, Luai Ji, Wanshu Wang, Lu Gao, Fu Peng, Zhenlei Song
A visible light-induced radical coupling of β-amino iodides and enones has been developed. This transformation offers efficient access to 1,5-amino ketones (25 examples, 71-96% yield), which serve as versatile precursors for the construction of cis-2,6-disubstituted piperidines. By integrating continuous-flow chemistry, the process becomes amenable to scale-up, affording higher yields and shorter reaction times compared to conventional batch reactions in flasks. The synthetic utility of this methodology was demonstrated through concise and symmetric total syntheses of cis-2,6-piperidine alkaloids, including H3 receptor agonists and (-)-6-epi-porantheridine.
{"title":"Flow Chemistry-Assisted Visible Light-Induced Radical Addition of β-Amino Iodides with Enones en Route to Efficient Construction of cis-2,6-Piperidines","authors":"Yufan Yang, Dongxu Wang, Dongyang Jiang, Kaixuan Pan, Yingchen Wang, Luai Ji, Wanshu Wang, Lu Gao, Fu Peng, Zhenlei Song","doi":"10.1039/d5qo01747e","DOIUrl":"https://doi.org/10.1039/d5qo01747e","url":null,"abstract":"A visible light-induced radical coupling of β-amino iodides and enones has been developed. This transformation offers efficient access to 1,5-amino ketones (25 examples, 71-96% yield), which serve as versatile precursors for the construction of cis-2,6-disubstituted piperidines. By integrating continuous-flow chemistry, the process becomes amenable to scale-up, affording higher yields and shorter reaction times compared to conventional batch reactions in flasks. The synthetic utility of this methodology was demonstrated through concise and symmetric total syntheses of cis-2,6-piperidine alkaloids, including H3 receptor agonists and (-)-6-epi-porantheridine.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146134070","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 regioselective functionalization of the C7 position of quinoline remains a formidable challenge due to its inherent electronic deactivation. Herein, we report an electrochemical strategy that enables divergent synthesis of valuable C7chlorinated and alkylated (arylated) quinolines from simple ortho-propynolaniline precursors. This method leverages electrooxidative dearomatization to generate key cyclohexadienimine intermediates, which undergo two distinct pathways dictated by the para-substituent: TMSCl-mediated cascade chlorination/cyclization delivers 4,7-dichloroquinolines, while substrates bearing para-alkyl/aryl groups (R 2 ≠ Me) undergo an aromatization-driven [1,2]-σ migration to furnish 4-chloro-7-alkyl/arylquinolines with high selectivity. This approach bypasses the reliance on pre-functionalized meta-chloroanilines substrates and hazardous chlorinating agents, operating under mild conditions. Gram-scale synthesis and further derivatizations highlight the practical utility of this method, offering a versatile and sustainable platform for constructing complex quinoline architectures.
{"title":"Electrochemically Enabled C7 Functionalization of Quinolines from o-Propynolanilines: Divergent Access to 4,7-Dichloro and 4-Chloro-7-alkyl (aryl) Quinolines","authors":"Xin Feng, Qiuqin He, Renhua Fan, Jiwen He","doi":"10.1039/d5qo01687h","DOIUrl":"https://doi.org/10.1039/d5qo01687h","url":null,"abstract":"The regioselective functionalization of the C7 position of quinoline remains a formidable challenge due to its inherent electronic deactivation. Herein, we report an electrochemical strategy that enables divergent synthesis of valuable C7chlorinated and alkylated (arylated) quinolines from simple ortho-propynolaniline precursors. This method leverages electrooxidative dearomatization to generate key cyclohexadienimine intermediates, which undergo two distinct pathways dictated by the para-substituent: TMSCl-mediated cascade chlorination/cyclization delivers 4,7-dichloroquinolines, while substrates bearing para-alkyl/aryl groups (R 2 ≠ Me) undergo an aromatization-driven [1,2]-σ migration to furnish 4-chloro-7-alkyl/arylquinolines with high selectivity. This approach bypasses the reliance on pre-functionalized meta-chloroanilines substrates and hazardous chlorinating agents, operating under mild conditions. Gram-scale synthesis and further derivatizations highlight the practical utility of this method, offering a versatile and sustainable platform for constructing complex quinoline architectures.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146134069","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}
Fluorine-containing organic molecules have been widely utilized in the fields of medicinal chemistry, synthetic chemistry, agrochemistry and materials science, due to their higher lipophilicity, metabolic stability, cell membrane permeability, bioactivity, and other advantageous properties. Among these, gem-difluoroalkenes have emerged as privileged carbonyl bioisosteres in drug design, exemplified by antimalarial difluoroartemisinin derivatives. Recent breakthroughs in visible-light photocatalysis have enabled mild, radical-mediated allylic defluorination of these substrates through single-electron transfer (SET) processes followed by β-fluorine elimination. This review highlights cutting-edge photochemical strategies (2022-2025) for constructing gem-difluoroalkenes, emphasizing mechanistic insights and functional group compatibility. The development of these sustainable methods addresses critical challenges in fluoroorganic synthesis while expanding accessible molecular diversity for medicinal applications.
{"title":"Recent Advances in Visible-Light-Induced Defluorinative Functionalization of α-Trifluoromethyl Arylalkenes","authors":"Yanyan He, Leiyang Lv, Zhenhua Jia, Teck Peng Loh","doi":"10.1039/d5qo01732g","DOIUrl":"https://doi.org/10.1039/d5qo01732g","url":null,"abstract":"Fluorine-containing organic molecules have been widely utilized in the fields of medicinal chemistry, synthetic chemistry, agrochemistry and materials science, due to their higher lipophilicity, metabolic stability, cell membrane permeability, bioactivity, and other advantageous properties. Among these, gem-difluoroalkenes have emerged as privileged carbonyl bioisosteres in drug design, exemplified by antimalarial difluoroartemisinin derivatives. Recent breakthroughs in visible-light photocatalysis have enabled mild, radical-mediated allylic defluorination of these substrates through single-electron transfer (SET) processes followed by β-fluorine elimination. This review highlights cutting-edge photochemical strategies (2022-2025) for constructing gem-difluoroalkenes, emphasizing mechanistic insights and functional group compatibility. The development of these sustainable methods addresses critical challenges in fluoroorganic synthesis while expanding accessible molecular diversity for medicinal applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122485","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}
We report an aerobic three-component reaction of isatoic anhydrides, anilines, and acrylamides that simultaneously forms two distinct C–N bonds through two sequential Pd(II)-catalyzed cycles, affording 2,3-dihydroquinazolin-4(1H)-ones (DHQs) incorporating β-amino carbonyl motifs. The presence of O2 is essential for chemoselective formation of DHQs; in its absence, the reaction instead affords the competing aza-Michael adduct. To understand the origin of this chemoselectivity, we investigated the mechanistic details of the reaction using DFT calculations. Our results reveal that, in the pathway leading to DHQs, the first C–N bond is formed through a Pd(II)-catalyzed oxidative C–H/N–H coupling, for which O2 is indispensable. O2 reacts with a Pd–H intermediate formed in the cycle, generating a Pd–hydroperoxide species that promotes catalyst turnover via H2O2 release. The second C–N bond is then formed through an intramolecular nucleophilic addition, furnishing the cyclic DHQ scaffold.
{"title":"Pd(II)-Catalyzed Aerobic Dual C–N Bond Formation: Oxygen-Dependent Divergence between Dihydroquinazolinone and Aza-Michael Pathways, an Experimental and Computational Study","authors":"Narges Mohammadi, Farnaz Jafarpour, Leyla Mohammadkhani, Alireza Ariafard","doi":"10.1039/d5qo01381j","DOIUrl":"https://doi.org/10.1039/d5qo01381j","url":null,"abstract":"We report an aerobic three-component reaction of isatoic anhydrides, anilines, and acrylamides that simultaneously forms two distinct C–N bonds through two sequential Pd(II)-catalyzed cycles, affording 2,3-dihydroquinazolin-4(1H)-ones (DHQs) incorporating β-amino carbonyl motifs. The presence of O2 is essential for chemoselective formation of DHQs; in its absence, the reaction instead affords the competing aza-Michael adduct. To understand the origin of this chemoselectivity, we investigated the mechanistic details of the reaction using DFT calculations. Our results reveal that, in the pathway leading to DHQs, the first C–N bond is formed through a Pd(II)-catalyzed oxidative C–H/N–H coupling, for which O2 is indispensable. O2 reacts with a Pd–H intermediate formed in the cycle, generating a Pd–hydroperoxide species that promotes catalyst turnover via H2O2 release. The second C–N bond is then formed through an intramolecular nucleophilic addition, furnishing the cyclic DHQ scaffold.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"133 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139049","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：