Covalent organic frameworks (COFs) have emerged as promising photocatalysts for H2O2 production due to their periodic and tunable structures. However, their photocatalytic performance is often limited by inefficient exciton dissociation and charge transport. Herein, three highly conjugated three-dimensional (3D) COFs with donor-acceptor (D-A) structures were synthesized to promote the photogenerated electron-hole separation and transport. To further enhance photocatalytic efficiency, electron-rich thiophene units were incorporated into the pore walls. Among the synthesized COFs, thiophene-modified COF-2 demonstrated an exceptional H2O2 generation rate of 10.68 mmol g-1 h-1 using 10% benzyl alcohol as a sacrificial agent, approximately 2.6 times higher than that of COF-1(4.12 mmol g-1 h-1) devoid of substituents. Interestingly, COF-3, featuring more extended conjugation through thianaphthene substituents, failed to achieve a higher H2O2 generation rate. Experimental characterizations confirmed that the superior performance of COF-2 originates from improved charge separation and transport, while theoretical analyses revealed that pore wall engineering significantly regulates the excited-state properties of 3D COFs. This work provides new insights into the molecular-level design of efficient 3D COF-based photocatalysts for sustainable H2O2 production.
{"title":"Pore Wall Engineering of Conjugated Three-Dimensional Covalent Organic Frameworks for Enhanced Hydrogen Peroxide Photosynthesis","authors":"Xin Zhao, Guoye Yu, Xuhan Zheng, Yuanping Yi, Guangchao Han, Yingjie Zhao, Yuancheng Wang","doi":"10.31635/ccschem.025.202506831","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506831","url":null,"abstract":"Covalent organic frameworks (COFs) have emerged as promising photocatalysts for H<sub>2</sub>O<sub>2</sub> production due to their periodic and tunable structures. However, their photocatalytic performance is often limited by inefficient exciton dissociation and charge transport. Herein, three highly conjugated three-dimensional (3D) COFs with donor-acceptor (D-A) structures were synthesized to promote the photogenerated electron-hole separation and transport. To further enhance photocatalytic efficiency, electron-rich thiophene units were incorporated into the pore walls. Among the synthesized COFs, thiophene-modified COF-2 demonstrated an exceptional H<sub>2</sub>O<sub>2</sub> generation rate of 10.68 mmol g<sup>-1</sup> h<sup>-1</sup> using 10% benzyl alcohol as a sacrificial agent, approximately 2.6 times higher than that of COF-1(4.12 mmol g<sup>-1</sup> h<sup>-1</sup>) devoid of substituents. Interestingly, COF-3, featuring more extended conjugation through thianaphthene substituents, failed to achieve a higher H<sub>2</sub>O<sub>2</sub> generation rate. Experimental characterizations confirmed that the superior performance of COF-2 originates from improved charge separation and transport, while theoretical analyses revealed that pore wall engineering significantly regulates the excited-state properties of 3D COFs. This work provides new insights into the molecular-level design of efficient 3D COF-based photocatalysts for sustainable H<sub>2</sub>O<sub>2</sub> production.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"20 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717425","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}
Helicoidal structures, inherently chiral when adopting a preferred-handed conformation, hold great promise for a variety of applications. However, the rational design and synthesis of helicoidal structures with controlled handedness at the molecular level remain formidable challenges, which further limit the comprehensive understanding of multiscale chirality transfer within such hierarchical systems. Herein, we incorporated (−)/(+)-pineno-fused 2,2′:6′,2″-terpyridine into polymer backbones, and constructed metallo-helicoids with preferred-handed conformations. Chiroptical studies and direct visualization of the screw-sense of metallo-helicoids elucidate the hierarchical chirality transfer, ranging from chiral center to coordination junction, helicoidal surface, entire helicoidal backbone, assembly of multiple helicoid chains, and ultimately extending to interactions with achiral guests. Moreover, super-helices as several strands of metallo-helicoid chains were reversibly formed by treating/removing water from the polymer solution, leading to an inverse screw-sense compared with individual metallo-helicoids. Such super-helices are further able to induce the chiroptical activity of achiral dye molecules via intermolecular electrostatic interactions, thereby resulting in a significant enhancement of circularly polarized luminescence. Our study not only enables precise control over the handedness of metallo-helicoids but also serves as an ideal platform for investigating chirality transfer across a wide range of length scales.
{"title":"Hierarchical Chirality Transfer and Reversible Chiroptical Switching in Metallo-Helicoids","authors":"Feng Su, Yinzhi Zhu, Runxu Tang, Shunran Zhang, Wenjing Zhang, Zhengong Meng, Weijia Wu, Yue Wu, Fang Fang, Zhi Chen, Haifeng Dong, Heng Wang, Xiujun Yu, Xiaopeng Li","doi":"10.31635/ccschem.025.202506664","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506664","url":null,"abstract":"Helicoidal structures, inherently chiral when adopting a preferred-handed conformation, hold great promise for a variety of applications. However, the rational design and synthesis of helicoidal structures with controlled handedness at the molecular level remain formidable challenges, which further limit the comprehensive understanding of multiscale chirality transfer within such hierarchical systems. Herein, we incorporated (−)/(+)-pineno-fused 2,2′:6′,2″-terpyridine into polymer backbones, and constructed metallo-helicoids with preferred-handed conformations. Chiroptical studies and direct visualization of the screw-sense of metallo-helicoids elucidate the hierarchical chirality transfer, ranging from chiral center to coordination junction, helicoidal surface, entire helicoidal backbone, assembly of multiple helicoid chains, and ultimately extending to interactions with achiral guests. Moreover, super-helices as several strands of metallo-helicoid chains were reversibly formed by treating/removing water from the polymer solution, leading to an inverse screw-sense compared with individual metallo-helicoids. Such super-helices are further able to induce the chiroptical activity of achiral dye molecules via intermolecular electrostatic interactions, thereby resulting in a significant enhancement of circularly polarized luminescence. Our study not only enables precise control over the handedness of metallo-helicoids but also serves as an ideal platform for investigating chirality transfer across a wide range of length scales.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"38 1","pages":"1-16"},"PeriodicalIF":11.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711592","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}
Pub Date : 2025-12-09DOI: 10.31635/ccschem.025.202506709
Ke-Xuan Du, Yi-Fan Chen, Zi-Han He, Ping Fang, Cong Ma, Niankai Fu, Youai Qiu, Tian-Sheng Mei
Organometallic electrochemical synthesis (OES), which combines electrochemistry with transition metal catalysis, has made remarkable headway. It employs electric current as a “traceless” redox agent, which is not only environmentally friendly and renewable but also permits the regulation of metal oxidation states. Moreover, by leveraging the tunable oxidation states, electronic properties, and steric characteristics of metal catalysts, this approach enables precise control over reaction chemoselectivity, regioselectivity, and stereoselectivity. In contrast to traditional metal-catalyzed reactions that depend on stoichiometric redox reagents, this method obviates the need for such additives, potentially enhancing its practical utility. In this mini review, we summarize recent advancements in nickel catalysis integrated with electrochemistry, with a focus on carbon–carbon (C–C) and carbon–heteroatom (C–Y) bond-forming reactions. Specifically, we first spotlight recent instances of electroreductive cross-couplings for C(sp2)–C(sp2), C(sp2)–C(sp3), and C(sp3)–C(sp3) bonds. Subsequently, we introduce several examples of electrophile π-addition, three-component reductive cross-couplings, and carboxylation. Finally, we describe C–Y bond formation, including C–O, C–N, C–S, and C–P bonds. These achievements may pave the way for breakthroughs in novel reactions, mechanistic understanding, and new synthetic modes in the field of OES.
{"title":"Recent Advances on Nickel-Catalyzed Electrochemical Couplings","authors":"Ke-Xuan Du, Yi-Fan Chen, Zi-Han He, Ping Fang, Cong Ma, Niankai Fu, Youai Qiu, Tian-Sheng Mei","doi":"10.31635/ccschem.025.202506709","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506709","url":null,"abstract":"Organometallic electrochemical synthesis (OES), which combines electrochemistry with transition metal catalysis, has made remarkable headway. It employs electric current as a “traceless” redox agent, which is not only environmentally friendly and renewable but also permits the regulation of metal oxidation states. Moreover, by leveraging the tunable oxidation states, electronic properties, and steric characteristics of metal catalysts, this approach enables precise control over reaction chemoselectivity, regioselectivity, and stereoselectivity. In contrast to traditional metal-catalyzed reactions that depend on stoichiometric redox reagents, this method obviates the need for such additives, potentially enhancing its practical utility. In this mini review, we summarize recent advancements in nickel catalysis integrated with electrochemistry, with a focus on carbon–carbon (C–C) and carbon–heteroatom (C–Y) bond-forming reactions. Specifically, we first spotlight recent instances of electroreductive cross-couplings for C(sp<sup>2</sup>)–C(sp<sup>2</sup>), C(sp<sup>2</sup>)–C(sp<sup>3</sup>), and C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bonds. Subsequently, we introduce several examples of electrophile π-addition, three-component reductive cross-couplings, and carboxylation. Finally, we describe C–Y bond formation, including C–O, C–N, C–S, and C–P bonds. These achievements may pave the way for breakthroughs in novel reactions, mechanistic understanding, and new synthetic modes in the field of OES.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"8 1","pages":"1-22"},"PeriodicalIF":11.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711591","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 switchable divergent strain-release/rearrangement cascade of bicyclo[1.1.0]butanes (BCBs), enabled by monoatomic oxygen or nitrogen insertion. Four distinct molecular scaffolds are accessed via the condition-dependent cascades: oxygen insertion affords β-methylene carbonyls via oxa-bicyclo[1.1.1]pentane-mediated ring opening and decarbonylation, itaconate derivatives via Grob-type ring opening, and cis-cyclopropanes via ring contraction; nitrogen insertion, in contrast, triggers ring expansion to form 2,4-disubstituted pyrroles. This strategy rapidly delivers bioactive-like frameworks with broad functional group tolerance. Synthetic utility is demonstrated by modular synthesis of bioactive molecules such as Esonarimod, Ralfuranone, and Rubrolide E. Mechanistic studies reveal that the position of the leaving group, whether on the heteroatom itself, the β-carbon, or the γ-carbon, within heteroatom-substituted cyclobutane intermediates dictates the divergent outcomes. These results establish a conceptually novel heteroatom-mediated strategy for programmable strain-release/rearrangement cascades, significantly expanding the reactivity profile of BCBs.
{"title":"Switchable Divergent Strain-Release/Rearrangement Cascades of Bicyclo[1.1.0]butanes Enabled by Monoatomic O/N Insertion","authors":"Jian Zhang, Ling Chen, Jun-Cheng Jin, Qi-Guo Zheng, Hanliang Zheng, Wei-Ping Deng","doi":"10.31635/ccschem.025.202506761","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506761","url":null,"abstract":"Herein, we report a switchable divergent strain-release/rearrangement cascade of bicyclo[1.1.0]butanes (BCBs), enabled by monoatomic oxygen or nitrogen insertion. Four distinct molecular scaffolds are accessed via the condition-dependent cascades: oxygen insertion affords β-methylene carbonyls via <i>oxa</i>-bicyclo[1.1.1]pentane-mediated ring opening and decarbonylation, itaconate derivatives via Grob-type ring opening, and <i>cis</i>-cyclopropanes via ring contraction; nitrogen insertion, in contrast, triggers ring expansion to form 2,4-disubstituted pyrroles. This strategy rapidly delivers bioactive-like frameworks with broad functional group tolerance. Synthetic utility is demonstrated by modular synthesis of bioactive molecules such as <i>Esonarimod</i>, <i>Ralfuranone</i>, and <i>Rubrolide E</i>. Mechanistic studies reveal that the position of the leaving group, whether on the heteroatom itself, the β-carbon, or the γ-carbon, within heteroatom-substituted cyclobutane intermediates dictates the divergent outcomes. These results establish a conceptually novel heteroatom-mediated strategy for programmable strain-release/rearrangement cascades, significantly expanding the reactivity profile of BCBs.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"11 1","pages":"1-15"},"PeriodicalIF":11.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145746684","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}
Molecular diodes, which enable directional charge transport at the single-molecule scale, are pivotal components for logic operations in molecular electronics, showing promise for future energy-efficient devices and ultracompact circuits. However, achieving high-performance molecular diodes with high rectification ratios (RR), operation stability, and reliable interconnections for logic operations still remains challenging. Recent advancements adopting noncovalent interactions to form supramolecular assemblies demonstrate promise in addressing this challenge by creating asymmetric electronic coupling while preserving efficient charge transport. In this review, we systematically summarize the designs of molecular diodes from single supramolecular junctions to self-assembled monolayer-based supramolecular junctions, and identify strategies using quantum interference to enhance the RR. These approaches provide valuable perspectives for high-performance single-molecule rectifiers through noncovalent supramolecular interactions, showcasing the potential of future bottom-up integration of molecular electronic devices.
{"title":"Supramolecular Diodes for Current Rectification","authors":"Yiqiang Jiang, Tianyue Zeng, Wei Xu, Hua Zhang, Zongyuan Xiao, Jia Shi, Junyang Liu, Wenjing Hong","doi":"10.31635/ccschem.025.202506481","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506481","url":null,"abstract":"Molecular diodes, which enable directional charge transport at the single-molecule scale, are pivotal components for logic operations in molecular electronics, showing promise for future energy-efficient devices and ultracompact circuits. However, achieving high-performance molecular diodes with high rectification ratios (RR), operation stability, and reliable interconnections for logic operations still remains challenging. Recent advancements adopting noncovalent interactions to form supramolecular assemblies demonstrate promise in addressing this challenge by creating asymmetric electronic coupling while preserving efficient charge transport. In this review, we systematically summarize the designs of molecular diodes from single supramolecular junctions to self-assembled monolayer-based supramolecular junctions, and identify strategies using quantum interference to enhance the RR. These approaches provide valuable perspectives for high-performance single-molecule rectifiers through noncovalent supramolecular interactions, showcasing the potential of future bottom-up integration of molecular electronic devices.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"10 1","pages":"1-23"},"PeriodicalIF":11.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717296","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}
Pub Date : 2025-12-09DOI: 10.31635/ccschem.025.202506588
Cheng Zhang, Lidan Guo, Chuanbo Cong, Qiong Zhou, Xiangnan Sun
Organic semiconductors (OSCs) are expected to exhibit long spin lifetimes and spin diffusion lengths at room temperature owing to their inherent weak spin relaxation arising from the light-element carbon-based composition. These advantages position OSCs as a promising materials platform for spin-based information processing, which has driven the rapid development of organic spintronics, focusing on spin relaxation, spin transport, and multifunctional integration. In recent years, with the deepening understanding of spin transport and relaxation dynamics, the spin transport performance of OSCs has been significantly improved, achieving millisecond-level spin lifetime and hundred-nanometer-scale spin diffusion length. Concurrently, the chemical tunability of OSC structures has enabled unique optoelectronic, chiral, and hybrid interfacial functionalities, fostering the certainty of novel spin-related functional devices and accelerating the translation of organic spintronics toward practical applications. This minireview highlights strategies for designing high-performance spin-transport OSCs through chemical and aggregation structure engineering, summarizes recent progress in spin-related multifunctionalities enabled by OSCs, and concludes with the key challenges, along with prospects in this field.
{"title":"Organic Spintronic Materials: Recent Progress and Emerging Multifunctionalities","authors":"Cheng Zhang, Lidan Guo, Chuanbo Cong, Qiong Zhou, Xiangnan Sun","doi":"10.31635/ccschem.025.202506588","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506588","url":null,"abstract":"Organic semiconductors (OSCs) are expected to exhibit long spin lifetimes and spin diffusion lengths at room temperature owing to their inherent weak spin relaxation arising from the light-element carbon-based composition. These advantages position OSCs as a promising materials platform for spin-based information processing, which has driven the rapid development of organic spintronics, focusing on spin relaxation, spin transport, and multifunctional integration. In recent years, with the deepening understanding of spin transport and relaxation dynamics, the spin transport performance of OSCs has been significantly improved, achieving millisecond-level spin lifetime and hundred-nanometer-scale spin diffusion length. Concurrently, the chemical tunability of OSC structures has enabled unique optoelectronic, chiral, and hybrid interfacial functionalities, fostering the certainty of novel spin-related functional devices and accelerating the translation of organic spintronics toward practical applications. This minireview highlights strategies for designing high-performance spin-transport OSCs through chemical and aggregation structure engineering, summarizes recent progress in spin-related multifunctionalities enabled by OSCs, and concludes with the key challenges, along with prospects in this field.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"229 1","pages":"1-20"},"PeriodicalIF":11.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731801","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}
P-stereogenic oxacyclic phosphines are valuable ligands in homogeneous catalysis but remain difficult to access. Here, we describe a modular strategy using a robust ambiphilic phosphine reagent that enables tandem nucleophilic addition to aldehydes followed by intramolecular SNAr cyclization. This protocol allows the rapid assembly of structurally diverse oxacyclic phosphine scaffolds with broad substrate scope under mild conditions. Asymmetric synthesis is also achieved, affording P-stereogenic products in high yields and excellent diastereoselectivity, without the need for redox manipulations or chiral resolution. Unlike previous methods that are limited to monophosphine or C2-symmetric bis-phosphine motifs, this platform provides access to a wide array of architecturally distinct ligands. The utility of this strategy is demonstrated in racemic C–C, C–N, and C–O bond-forming reactions, as well as enantioselective hydrogenation and cross-coupling. Mechanistic studies reveal that the high diastereoselectivity originates from a Curtin–Hammett-type scenario, in which the SNAr cyclization step is governed by the relative energies of competing transition states.
{"title":"Redox-Free and Modular Access to Oxacyclic Phosphines Enabled by a Robust Ambiphilic Phosphine Reagent","authors":"Bin Lu, Jianchao Yu, Hao Sun, Renwei Xiao, Ruonan Chen, Xumu Zhang, Gen-Qiang Chen","doi":"10.31635/ccschem.025.202506531","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506531","url":null,"abstract":"P-stereogenic oxacyclic phosphines are valuable ligands in homogeneous catalysis but remain difficult to access. Here, we describe a modular strategy using a robust ambiphilic phosphine reagent that enables tandem nucleophilic addition to aldehydes followed by intramolecular S<sub>N</sub>Ar cyclization. This protocol allows the rapid assembly of structurally diverse oxacyclic phosphine scaffolds with broad substrate scope under mild conditions. Asymmetric synthesis is also achieved, affording P-stereogenic products in high yields and excellent diastereoselectivity, without the need for redox manipulations or chiral resolution. Unlike previous methods that are limited to monophosphine or C<sub>2</sub>-symmetric bis-phosphine motifs, this platform provides access to a wide array of architecturally distinct ligands. The utility of this strategy is demonstrated in racemic C–C, C–N, and C–O bond-forming reactions, as well as enantioselective hydrogenation and cross-coupling. Mechanistic studies reveal that the high diastereoselectivity originates from a Curtin–Hammett-type scenario, in which the S<sub>N</sub>Ar cyclization step is governed by the relative energies of competing transition states.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"141 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717294","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}
Pub Date : 2025-12-09DOI: 10.31635/ccschem.025.202506704
Binghong Teng, Yunliang Guo, Lan Hu, Lihan Zhu, Kehan Jiao, Tao Xiong, Guangfan Zheng, Qian Zhang
The ipso- and remote C–H difunctionalization of substituted arenes offers a powerful strategy for introducing diverse functional groups into aromatic scaffolds while enabling multisite modifications. Existing methodologies for arene difunctionalization, represented by the Catellani reaction, are constrained by limited control over ipso/ortho-selectivity and exclusive applicability to activated arene substrates. Particularly, the development of reliable strategies for ipso/para-difunctionalization of substituted arenes via dual inert bond activations continues to present a formidable challenge in modern synthetic chemistry. Herein, we present a visible-light-mediated, photoredox-catalyzed radical-polar ipso, para-difunctionalization of aniline derivatives through delayed aryl migration. CF2HSO2Na acts as a bifunctional reagent delivering CF2H radicals and SO2. Rapid and reversible trapping of a catalytic amount of SO2 with cyclohexadienyl radicals generated from ipso-addition interrupts the radical-type aryl migration, promoting unprecedented ipso/para- difunctionalization of arenes through a sequential para-functionalization/ionic C–N bond cleavage cascade. Polyfluoroarenes serve as efficient terminating reagents to promote rapid transformation of metastable cyclohexadienyl sulfonyl anion within dynamic equilibrium systems. This methodology delays traditional aryl migration pathways through the incorporation of para-functionalization events, achieving concurrent activation of the inert C–N and para-C–H bond in a stepwise manner.
{"title":"Photoredox-Induced Radical-Polar Crossover ipso, para-Difunctionalization of Aniline Derivatives via Delayed Aryl Migration","authors":"Binghong Teng, Yunliang Guo, Lan Hu, Lihan Zhu, Kehan Jiao, Tao Xiong, Guangfan Zheng, Qian Zhang","doi":"10.31635/ccschem.025.202506704","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506704","url":null,"abstract":"The<i> ipso-</i> and remote C–H difunctionalization of substituted arenes offers a powerful strategy for introducing diverse functional groups into aromatic scaffolds while enabling multisite modifications. Existing methodologies for arene difunctionalization, represented by the Catellani reaction, are constrained by limited control over <i>ipso</i>/<i>ortho</i>-selectivity and exclusive applicability to activated arene substrates. Particularly, the development of reliable strategies for <i>ipso/para</i>-difunctionalization of substituted arenes via dual inert bond activations continues to present a formidable challenge in modern synthetic chemistry. Herein, we present a visible-light-mediated, photoredox-catalyzed radical-polar <i>ipso, para-</i>difunctionalization of aniline derivatives through delayed aryl migration. CF<sub>2</sub>HSO<sub>2</sub>Na acts as a bifunctional reagent delivering CF<sub>2</sub>H radicals and SO<sub>2</sub>. Rapid and reversible trapping of a catalytic amount of SO<sub>2</sub> with cyclohexadienyl radicals generated from <i>ipso</i>-addition interrupts the radical-type aryl migration, promoting unprecedented <i>ipso/para</i>- difunctionalization of arenes through a sequential <i>para-</i>functionalization/ionic C–N bond cleavage cascade. Polyfluoroarenes serve as efficient terminating reagents to promote rapid transformation of metastable cyclohexadienyl sulfonyl anion within dynamic equilibrium systems. This methodology delays traditional aryl migration pathways through the incorporation of <i>para</i>-functionalization events, achieving concurrent activation of the inert C–N and <i>para</i>-C–H bond in a stepwise manner.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"15 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731803","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}
Pub Date : 2025-12-08DOI: 10.31635/ccschem.025.202506372
Wei Zhou, C. S. Praveen, Wei Wang, Chenxi He, Takashi Toyao, Ken-ichi Shimizu, Ryo Toyoshima, Hiroshi Kondoh, Yuhao Wang, Chunliang Wang, James Paterson, Jamie Southouse, Carlo Federico Pauletti, Aleix Comas-Vives, Christophe Copéret
Controlling the selectivity of CO2 hydrogenation remains a challenge in catalysis. In this study, we demonstrated that the well-defined silica(SiO2)-supported PtGa and PtZn alloy nanoparticles, synthesized via a surface organometallic chemistry (SOMC) approach, displayed greatly different product selectivity in CO2 hydrogenation: While the PtZn@SiO2 catalyst showed almost exclusive CO selectivity (∼99%), PtGa@SiO2 primarily produced CH3OH with 54% selectivity, despite both catalysts showing similar activities. While both PtM (M = Zn or Ga) formed bulk alloys, in situ spectroscopic studies complemented with density functional theory (DFT) calculations revealed that their surface properties differed under reaction conditions, determining the product selectivity. The surface of the PtZn alloy remained stable without undergoing surface oxidation during CO2 hydrogenation, resulting in the decomposition of formate (HCOO*) species to produce CO. In contrast, the surface of the PtGa alloy underwent a dynamic redox process, forming PtGa-GaOx interfaces under defined reaction conditions, which was key to promoting methanol synthesis via a HCOO*→CH3O* reaction pathway.
{"title":"PtZn Versus PtGa in CO2 Hydrogenation: When Alloy Stability and Redox Dynamics Drive Selectivity","authors":"Wei Zhou, C. S. Praveen, Wei Wang, Chenxi He, Takashi Toyao, Ken-ichi Shimizu, Ryo Toyoshima, Hiroshi Kondoh, Yuhao Wang, Chunliang Wang, James Paterson, Jamie Southouse, Carlo Federico Pauletti, Aleix Comas-Vives, Christophe Copéret","doi":"10.31635/ccschem.025.202506372","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506372","url":null,"abstract":"Controlling the selectivity of CO<sub>2</sub> hydrogenation remains a challenge in catalysis. In this study, we demonstrated that the well-defined silica(SiO<sub>2</sub>)-supported PtGa and PtZn alloy nanoparticles, synthesized via a surface organometallic chemistry (SOMC) approach, displayed greatly different product selectivity in CO<sub>2</sub> hydrogenation: While the PtZn@SiO<sub>2</sub> catalyst showed almost exclusive CO selectivity (∼99%), PtGa@SiO<sub>2</sub> primarily produced CH<sub>3</sub>OH with 54% selectivity, despite both catalysts showing similar activities. While both Pt<i>M</i> (<i>M</i> = Zn or Ga) formed bulk alloys, in situ spectroscopic studies complemented with density functional theory (DFT) calculations revealed that their surface properties differed under reaction conditions, determining the product selectivity. The surface of the PtZn alloy remained stable without undergoing surface oxidation during CO<sub>2</sub> hydrogenation, resulting in the decomposition of formate (HCOO*) species to produce CO. In contrast, the surface of the PtGa alloy underwent a dynamic redox process, forming PtGa-GaO<sub>x</sub> interfaces under defined reaction conditions, which was key to promoting methanol synthesis via a HCOO*→CH<sub>3</sub>O* reaction pathway.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"113 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711593","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}
Skeletal editing, especially for nitrogen-containing aromatic heterocycles, has become an increasingly important strategy for drug modification and development, enabling rapid compound diversification without the need for de novo synthesis. Notably, despite their pervasiveness, established methods fall short in selective atomic swap due to the high stability of aromatic compounds. In this study, we report a CN-to-S atom swap approach for direct skeletal editing of pyridines into thiophenes via the addition of nucleophiles, ring-opening, and ring-closing (ANRORC) processes. Elemental sulfur, acting as an amphiphilic reagent, mediated this process through successive electrophilic and nucleophilic addition of the central sulfur atom at predictable sites. The power of this skeletal editing strategy was highlighted through the modification of the frameworks of natural products and drug molecules in a precise and controllable manner.
{"title":"Skeletal Editing of Pyridines to Thiophene-2-Carbaldehydes","authors":"Cong Lv, Shenxiang Wang, Yonglin Shi, Meixin Yan, Jing Zhang, Yufeng Wan, Shun Li, Dexi Yang, Shunyao Huang, Jiangui Zhao, Weichao Xue, Jiaqi Xu, Xueli Zheng, Ruixiang Li, Hua Chen, Haiyan Fu","doi":"10.31635/ccschem.025.202506485","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506485","url":null,"abstract":"Skeletal editing, especially for nitrogen-containing aromatic heterocycles, has become an increasingly important strategy for drug modification and development, enabling rapid compound diversification without the need for de novo synthesis. Notably, despite their pervasiveness, established methods fall short in selective atomic swap due to the high stability of aromatic compounds. In this study, we report a CN-to-S atom swap approach for direct skeletal editing of pyridines into thiophenes via the addition of nucleophiles, ring-opening, and ring-closing (ANRORC) processes. Elemental sulfur, acting as an amphiphilic reagent, mediated this process through successive electrophilic and nucleophilic addition of the central sulfur atom at predictable sites. The power of this skeletal editing strategy was highlighted through the modification of the frameworks of natural products and drug molecules in a precise and controllable manner.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"144 1","pages":"1-11"},"PeriodicalIF":11.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145717295","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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