Mechanophoric hydrogels undergo visible color changes or alterations in optical properties in response to mechanical stimuli. Achieving mechanophoric features in hydrogel materials involves careful control of the polymer microstructure, as well as the incorporation of mechanoresponsive molecular entities known as mechanophores. Upon mechanical activation, mechanophores undergo reversible or irreversible molecular rearrangements, leading to a visual response. This review serves as a practical reference for selecting and designing mechanophores, and classifies their mode of action. By consolidating key information on molecular and materials design criteria, it focuses specifically on mechanophoric responses within hydrogel networks and provides insight into pioneering contributions, as well as some of the most recent advances and literature examples. The multidisciplinary nature of this rapidly growing research field requires expertise in organic synthesis, physical polymer chemistry and photophysics, making this review a valuable resource for researchers interested in the fundamental developments or applications of mechanophoric hydrogel materials.
{"title":"Mechanophoric hydrogels: when mechanical stress produces useful responses","authors":"Franciela Arenhart Soares, Pol Besenius","doi":"10.1039/d4qo02060j","DOIUrl":"https://doi.org/10.1039/d4qo02060j","url":null,"abstract":"Mechanophoric hydrogels undergo visible color changes or alterations in optical properties in response to mechanical stimuli. Achieving mechanophoric features in hydrogel materials involves careful control of the polymer microstructure, as well as the incorporation of mechanoresponsive molecular entities known as mechanophores. Upon mechanical activation, mechanophores undergo reversible or irreversible molecular rearrangements, leading to a visual response. This review serves as a practical reference for selecting and designing mechanophores, and classifies their mode of action. By consolidating key information on molecular and materials design criteria, it focuses specifically on mechanophoric responses within hydrogel networks and provides insight into pioneering contributions, as well as some of the most recent advances and literature examples. The multidisciplinary nature of this rapidly growing research field requires expertise in organic synthesis, physical polymer chemistry and photophysics, making this review a valuable resource for researchers interested in the fundamental developments or applications of mechanophoric hydrogel materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435253","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 report, we describe a nickel-free, zinc-induced reductive coupling between (hetero)aryl diazonium salts and electrophilic chalcogen species under mild reaction conditions. This nonbasic protocol offers excellent chemoselectivity and substrate tolerance, yielding a broad spectrum of unsymmetrical diaryl and aryl–alkyl chalcogenides with good to excellent yields. Moreover, scale-up reactions, late-stage modifications of bioactive molecules and versatile product derivations have been conducted to showcase the practicality of this system. Preliminary mechanistic studies suggest the involvement of a single-electron transfer (SET) process from zinc to diazonium salts or the formation of zinc thiolate via oxidative addition of S–S bonds, revealing the versatile roles of zinc in this Sandmeyer-type sulfuration, which has been rarely studied.
{"title":"Zn-promoted Sandmeyer-type reductive chalcogenation of (hetero)aryl diazonium salts","authors":"Qiujin Fan, Yanchuang Zhao, Junhong Wang, Ying Bai, Shengbin Zhou, Xinxin Shao","doi":"10.1039/d5qo00103j","DOIUrl":"https://doi.org/10.1039/d5qo00103j","url":null,"abstract":"In this report, we describe a nickel-free, zinc-induced reductive coupling between (hetero)aryl diazonium salts and electrophilic chalcogen species under mild reaction conditions. This nonbasic protocol offers excellent chemoselectivity and substrate tolerance, yielding a broad spectrum of unsymmetrical diaryl and aryl–alkyl chalcogenides with good to excellent yields. Moreover, scale-up reactions, late-stage modifications of bioactive molecules and versatile product derivations have been conducted to showcase the practicality of this system. Preliminary mechanistic studies suggest the involvement of a single-electron transfer (SET) process from zinc to diazonium salts or the formation of zinc thiolate <em>via</em> oxidative addition of S–S bonds, revealing the versatile roles of zinc in this Sandmeyer-type sulfuration, which has been rarely studied.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435254","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}
Honglin Qiu, Jiadong Zhou, Yi Feng, Linlin Liu, Zengqi Xie
This article presents the successful synthesis of a novel series of core-extended quasi-planar nonastarazine (NSA) derivatives, featuring diverse arm configurations, through one-pot sequential reactions. Analysis of their single-crystal structures reveals that the three arms are nearly coplanar, ensuring good conjugation for this series of molecules. The UV-vis absorption and photoluminescence spectra of these NSA derivatives indicate that their photophysical properties are primarily dominated by the extended arms, a finding supported by theoretical calculations of frontier orbital energy levels. The designable topological molecule structures and excellent fluorescence properties of these core-extended NSAs endow them high potentials for applications in molecular electronics.
{"title":"Core-Extended Nonastarazines Featuring Diverse Arm Configurations via One-Pot Sequential Reactions","authors":"Honglin Qiu, Jiadong Zhou, Yi Feng, Linlin Liu, Zengqi Xie","doi":"10.1039/d4qo02403f","DOIUrl":"https://doi.org/10.1039/d4qo02403f","url":null,"abstract":"This article presents the successful synthesis of a novel series of core-extended quasi-planar nonastarazine (NSA) derivatives, featuring diverse arm configurations, through one-pot sequential reactions. Analysis of their single-crystal structures reveals that the three arms are nearly coplanar, ensuring good conjugation for this series of molecules. The UV-vis absorption and photoluminescence spectra of these NSA derivatives indicate that their photophysical properties are primarily dominated by the extended arms, a finding supported by theoretical calculations of frontier orbital energy levels. The designable topological molecule structures and excellent fluorescence properties of these core-extended NSAs endow them high potentials for applications in molecular electronics.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435256","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}
Ya-Li Hu, Ding Dong, Jian-Jun Zhao, Kun Hu, Ling-Mei Kong, Yun-Xia Hu, Xing-Ren Li, Song-Yu Li, Yin Nian, Gang Xu
Ascynols A–C (1–3), three polycyclic polyprenylated acylphloroglucinol (PPAP) derivatives sharing an unusual cyclopentane core, were isolated from the aerial parts of Hypericum ascyron L. Compounds 1 and 3 were elucidated to possess two novel 6/6/5/5 and 5/5 architectures, respectively. Additionally, twenty-four analogues (4–27) were also obtained, among which fourteen are new compounds. These compounds represent 11 different structural types and can be categorized into 6 groups based on their biosynthetic origin. Their structures were determined from spectroscopic analysis, quantum chemical calculation, and X-ray diffraction data. All the isolates are decorated with a methyl group at C-5 instead of a prenyl or geranyl group as in most other PPAPs. Biologically, sixteen compounds were identified as potent inhibitors of low-voltage-gated calcium channels (LVGCCs; Cav3.1–3.3), with IC50 values ranging from 1.89 to 16.55 μmol L−1. Moreover, compound 23 exhibited strong and dose-dependent antinociception in an acetic acid-induced mouse model of visceral pain and its effect is comparable to that of Z944, a representative LVGCC inhibitor under clinical trial.
{"title":"5-Methylated polyprenylated acylphloroglucinol derivatives as low-voltage-gated Ca2+ channel inhibitors","authors":"Ya-Li Hu, Ding Dong, Jian-Jun Zhao, Kun Hu, Ling-Mei Kong, Yun-Xia Hu, Xing-Ren Li, Song-Yu Li, Yin Nian, Gang Xu","doi":"10.1039/d4qo02233e","DOIUrl":"https://doi.org/10.1039/d4qo02233e","url":null,"abstract":"Ascynols A–C (<strong>1–3</strong>), three polycyclic polyprenylated acylphloroglucinol (PPAP) derivatives sharing an unusual cyclopentane core, were isolated from the aerial parts of <em>Hypericum ascyron</em> L. Compounds <strong>1</strong> and <strong>3</strong> were elucidated to possess two novel 6/6/5/5 and 5/5 architectures, respectively. Additionally, twenty-four analogues (<strong>4–27</strong>) were also obtained, among which fourteen are new compounds. These compounds represent 11 different structural types and can be categorized into 6 groups based on their biosynthetic origin. Their structures were determined from spectroscopic analysis, quantum chemical calculation, and X-ray diffraction data. All the isolates are decorated with a methyl group at C-5 instead of a prenyl or geranyl group as in most other PPAPs. Biologically, sixteen compounds were identified as potent inhibitors of low-voltage-gated calcium channels (LVGCCs; Ca<small><sub>v</sub></small>3.1–3.3), with IC<small><sub>50</sub></small> values ranging from 1.89 to 16.55 μmol L<small><sup>−1</sup></small>. Moreover, compound <strong>23</strong> exhibited strong and dose-dependent antinociception in an acetic acid-induced mouse model of visceral pain and its effect is comparable to that of Z944, a representative LVGCC inhibitor under clinical trial.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"64 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427069","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}
Julio C. Flores-Reyes, Yoarhy A. Amador-Sánchez, Alejandro Valderrama-Celestino, Bertha Daniela Barrios-Campos, Ricardo A. Peralta, Michael Huxley, Ilich A. Ibarra, Alejandro Islas-Jácome, Diego Solis-Ibarra, Eduardo González-Zamora
The dual-state emission (DSE) phenomenon has become crucial for developing dual-state emission luminogens (DSEgens) that exhibit efficient luminescence in both solution and solid states, addressing the limitations of conventional, phase-restricted fluorophores. Compounds exhibiting excited-state intramolecular proton transfer (ESIPT) mechanisms are especially valuable for enhancing emission stability across these states, offering significant potential in optoelectronics, bioimaging, and sensing applications. In this study, we report the synthesis of six new pyrazolyl-pyrrolo[3,4-b]pyridin-5-ones through an Ugi-Zhu-3CR coupled to an aza-Diels-Alder/N-acylation/decarboxylation/dehydration cascade sequence. An x-ray ORTEP confirms unequivocally the structure of one of the synthesized compounds. These ones demonstrate intriguing photophysical properties such as large Stokes shifts (>11,900 cm⁻¹) in solution and robust solid-state emission via Excited-State Intramolecular Proton Transfer (ESIPT) mechanism. Complementary DFT and TD-DFT calculations confirm weak but allowed transitions involving both pyrazole and pyrrolo[3,4-b]pyridin-5-one moieties, in agreement with experimental observations. This work represents the first application of an isocyanide-based multicomponent reaction for DSEgen synthesis, paving the way for innovative advances in the design of organic luminescent materials.
{"title":"Dual-State Emission of Pyrazolyl-Pyrrolo[3,4-b]pyridin-5-ones via Excited-State Intramolecular Proton Transfer (ESIPT): Multicomponent Synthesis and Optical Characterization","authors":"Julio C. Flores-Reyes, Yoarhy A. Amador-Sánchez, Alejandro Valderrama-Celestino, Bertha Daniela Barrios-Campos, Ricardo A. Peralta, Michael Huxley, Ilich A. Ibarra, Alejandro Islas-Jácome, Diego Solis-Ibarra, Eduardo González-Zamora","doi":"10.1039/d4qo02256d","DOIUrl":"https://doi.org/10.1039/d4qo02256d","url":null,"abstract":"The dual-state emission (DSE) phenomenon has become crucial for developing dual-state emission luminogens (DSEgens) that exhibit efficient luminescence in both solution and solid states, addressing the limitations of conventional, phase-restricted fluorophores. Compounds exhibiting excited-state intramolecular proton transfer (ESIPT) mechanisms are especially valuable for enhancing emission stability across these states, offering significant potential in optoelectronics, bioimaging, and sensing applications. In this study, we report the synthesis of six new pyrazolyl-pyrrolo[3,4-b]pyridin-5-ones through an Ugi-Zhu-3CR coupled to an aza-Diels-Alder/N-acylation/decarboxylation/dehydration cascade sequence. An x-ray ORTEP confirms unequivocally the structure of one of the synthesized compounds. These ones demonstrate intriguing photophysical properties such as large Stokes shifts (>11,900 cm⁻¹) in solution and robust solid-state emission via Excited-State Intramolecular Proton Transfer (ESIPT) mechanism. Complementary DFT and TD-DFT calculations confirm weak but allowed transitions involving both pyrazole and pyrrolo[3,4-b]pyridin-5-one moieties, in agreement with experimental observations. This work represents the first application of an isocyanide-based multicomponent reaction for DSEgen synthesis, paving the way for innovative advances in the design of organic luminescent materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"80 1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435257","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}
Heteroaromatic installation and peripheral modifications are the most common reactions in the pharmaceutical industry. However, the synthesis of biologically important aminonitrile-functionalized heteroaromatics remains unexplored. Although nucleophilic aminonitrile introduction and Strecker reaction under enantioselective catalytic conditions enable facile access to chiral aminonitriles, these approaches largely disfavor substrates with highly steric substituents on the imine carbon atom, thus affording limited products. Herein, we report an efficient and versatile method that combines the traditional methods to generate α-aryl-α-heteroaryl-aminonitriles. This methodology exhibits a broad scope and can form bonds even when using low-reactive Friedel–Crafts nucleophiles through a mild and practical protocol. It should be highlighted that the catalyst loading could be reduced to parts per billion, giving rise to phenomenal turn-over-number (TON) and turn-over-frequency (TOF) values. Interestingly, different stereochemistries between the pyrrole and indole adducts were obtained with the same (R)-derived chiral phosphoric acid catalysis. Computational studies have indicated that this unpredicted stereoreversal is due to the coordination system between iminonitriles and catalysts, helping us understand the origin of the stereochemical outcome of the traditional Friedel–Crafts reaction.
{"title":"Enantioselective modular synthesis of α-aryl-α-heteroaryl aminonitriles with parts per million organocatalyst loading: mechanistic investigation for stereochemical origins","authors":"Yusuke Oyamada, Kaito Ishikawa, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura","doi":"10.1039/d4qo02362e","DOIUrl":"https://doi.org/10.1039/d4qo02362e","url":null,"abstract":"Heteroaromatic installation and peripheral modifications are the most common reactions in the pharmaceutical industry. However, the synthesis of biologically important aminonitrile-functionalized heteroaromatics remains unexplored. Although nucleophilic aminonitrile introduction and Strecker reaction under enantioselective catalytic conditions enable facile access to chiral aminonitriles, these approaches largely disfavor substrates with highly steric substituents on the imine carbon atom, thus affording limited products. Herein, we report an efficient and versatile method that combines the traditional methods to generate α-aryl-α-heteroaryl-aminonitriles. This methodology exhibits a broad scope and can form bonds even when using low-reactive Friedel–Crafts nucleophiles through a mild and practical protocol. It should be highlighted that the catalyst loading could be reduced to parts per billion, giving rise to phenomenal turn-over-number (TON) and turn-over-frequency (TOF) values. Interestingly, different stereochemistries between the pyrrole and indole adducts were obtained with the same (<em>R</em>)-derived chiral phosphoric acid catalysis. Computational studies have indicated that this unpredicted stereoreversal is due to the coordination system between iminonitriles and catalysts, helping us understand the origin of the stereochemical outcome of the traditional Friedel–Crafts reaction.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427068","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}
Diazo compounds are a class of readily available and versatile reagents in modern organic synthesis that have been used as valuable synthetic building blocks for a diverse range of important organic transformations due to their convenient preparation and high reactivity. In this review, the advancements in the synthesis of nitrogen-containing heterocycles via Rh(III)-catalyzed chelation-assisted tandem C-H activation/carbene insertion/annulation with diazo compounds as carbene precursors have been summarized. A variety of structurally diverse nitrogen heterocyclic scaffolds, such as indoles, isoindolones, carbazoles, isoquinolines, isoquinolones, 2H-indazoles, indazolones, cinnolines, 2,3-benzodiazepines, azepines, diazepinones can be easily prepared from different diazo compounds in a highly efficient and environmentally benign manner.
{"title":"Recent advances in the synthesis of nitrogen heterocycles via Rh(III)-catalyzed chelation-assisted C-H activation/annulation with diazo compounds","authors":"Jidan Liu, Ruilian Liang, Qinglian Yan, Liyao Zheng, Zhao-Qing Liu, Shouzhi Pu","doi":"10.1039/d5qo00111k","DOIUrl":"https://doi.org/10.1039/d5qo00111k","url":null,"abstract":"Diazo compounds are a class of readily available and versatile reagents in modern organic synthesis that have been used as valuable synthetic building blocks for a diverse range of important organic transformations due to their convenient preparation and high reactivity. In this review, the advancements in the synthesis of nitrogen-containing heterocycles via Rh(III)-catalyzed chelation-assisted tandem C-H activation/carbene insertion/annulation with diazo compounds as carbene precursors have been summarized. A variety of structurally diverse nitrogen heterocyclic scaffolds, such as indoles, isoindolones, carbazoles, isoquinolines, isoquinolones, 2H-indazoles, indazolones, cinnolines, 2,3-benzodiazepines, azepines, diazepinones can be easily prepared from different diazo compounds in a highly efficient and environmentally benign manner.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427067","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}
Guang-Chuan Xu, Liang Zeng, Ming Hu, Fujin Sun, Jin-Heng Li
A synthetically useful method for the formal β-heteroarylation of ketones via an iodoarene-directed photoredox remote C(sp3)−H heteroarylation of o-iodoarylalkan-1-ones with heteroarenes is reported. This protocol relies on single electron transfer (SET), hydrogen atom transfer (HAT) and dual C-H functionalizations leading to β-heteroaryl ketones. This mild method displays a broad scope, a good functional group compatibility, a high atom economy and an excellent selectivity control.
{"title":"Photoredox β-C(sp3)-H Heteroarylation of o-Iodoaryl-alkan-1-ones with Heteroarenes via HAT and Dual C-H Functionalizations","authors":"Guang-Chuan Xu, Liang Zeng, Ming Hu, Fujin Sun, Jin-Heng Li","doi":"10.1039/d5qo00147a","DOIUrl":"https://doi.org/10.1039/d5qo00147a","url":null,"abstract":"A synthetically useful method for the formal β-heteroarylation of ketones via an iodoarene-directed photoredox remote C(sp3)−H heteroarylation of o-iodoarylalkan-1-ones with heteroarenes is reported. This protocol relies on single electron transfer (SET), hydrogen atom transfer (HAT) and dual C-H functionalizations leading to β-heteroaryl ketones. This mild method displays a broad scope, a good functional group compatibility, a high atom economy and an excellent selectivity control.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418426","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}
Cheng Feng, Shouzhe Zhu, Shuang Yang, Feifei Xing, Xiang Wang
Transient assemblies generated by fuel consumption biomacromolecules are essential for biological processes. Although artificial transient assemblies have been investitigated extensively in recent years, molecules mimicking secondary structures of biomacromolecules have been rarely exploited to construct fuel driving transient systems. Herein, we reported a transient foldaxane system using a double helical aromatic oligoamide. The aromatic oligoamide adopts a mixture of parallel and antiparallel conformation in solution, whilst the presence of a molecular thread drives the conversion of parallel double helix to antiparallel double helix and the formation of foldaxane between antiparallel double helix and the thread. 4-Methylpiperidine can cleave the thread to regenerate free parallel and antiparallel double helix. The formation of foldaxane can be fueled with this thread for upto three cycles. These results open up a possibility to introduce dissipative behavior into abiotic quaternary structures to generate life-like dynamic systems.
{"title":"Dissipative formation of a transient foldaxane with a fuel-like thread","authors":"Cheng Feng, Shouzhe Zhu, Shuang Yang, Feifei Xing, Xiang Wang","doi":"10.1039/d4qo02092h","DOIUrl":"https://doi.org/10.1039/d4qo02092h","url":null,"abstract":"Transient assemblies generated by fuel consumption biomacromolecules are essential for biological processes. Although artificial transient assemblies have been investitigated extensively in recent years, molecules mimicking secondary structures of biomacromolecules have been rarely exploited to construct fuel driving transient systems. Herein, we reported a transient foldaxane system using a double helical aromatic oligoamide. The aromatic oligoamide adopts a mixture of parallel and antiparallel conformation in solution, whilst the presence of a molecular thread drives the conversion of parallel double helix to antiparallel double helix and the formation of foldaxane between antiparallel double helix and the thread. 4-Methylpiperidine can cleave the thread to regenerate free parallel and antiparallel double helix. The formation of foldaxane can be fueled with this thread for upto three cycles. These results open up a possibility to introduce dissipative behavior into abiotic quaternary structures to generate life-like dynamic systems.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418427","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}
Allylamines are a versatile class of compounds with significant applications in pharmaceuticals and as building blocks in organic synthesis. Herein we present a straightforward protocol of visible-light driven g-C3N4-catalyzed decarboxylative alkenylation of N‑aryl glycines with vinyl sulfones to access allylamines in moderate to excellent yields (up to 91%), which demonstrated broad substrate compatibility, inculding primary, secondary, tertiary N‑aryl glycines and diverse vinyl sulfones. Notably, the g-C3N4 catalyst is recyclable for up to five times without obvious loss of catalytic performance. Preliminary mechanistic studies indicated that the visible light is essential to achieve the desired transformation efficiently.
{"title":"Recyclable g-C3N4 Catalyzed Decarboxylative Alkenylation of N‑aryl Glycines with Vinyl Sulfones under Visible-Light Irradiation","authors":"Teck Peng Loh, Chengjie Guo, Guozhi Zhao, Yabiao Feng, Dong Chen, Dongping Wang, Zhenhua Jia","doi":"10.1039/d5qo00100e","DOIUrl":"https://doi.org/10.1039/d5qo00100e","url":null,"abstract":"Allylamines are a versatile class of compounds with significant applications in pharmaceuticals and as building blocks in organic synthesis. Herein we present a straightforward protocol of visible-light driven g-C3N4-catalyzed decarboxylative alkenylation of N‑aryl glycines with vinyl sulfones to access allylamines in moderate to excellent yields (up to 91%), which demonstrated broad substrate compatibility, inculding primary, secondary, tertiary N‑aryl glycines and diverse vinyl sulfones. Notably, the g-C3N4 catalyst is recyclable for up to five times without obvious loss of catalytic performance. Preliminary mechanistic studies indicated that the visible light is essential to achieve the desired transformation efficiently.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418429","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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