Organic chemistry frontiers : an international journal of organic chemistry最新文献_第6页

Enabling C–C bond-forming strategies for tailored derivatisation of heptazine frameworks 使C-C键形成策略适合于七嗪框架的衍生化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-03-31 DOI: 10.1039/d6qo00267f

Aurélien Huet , Benjamin Louis , Rana Deeba , Ahmed Ait Khouya , Yves Chenavier , Renaud Demadrille , Jacques Pécaut , Lionel Dubois , Julie Andrez

{"title":"Enabling C–C bond-forming strategies for tailored derivatisation of heptazine frameworks","authors":"Aurélien Huet , Benjamin Louis , Rana Deeba , Ahmed Ait Khouya , Yves Chenavier , Renaud Demadrille , Jacques Pécaut , Lionel Dubois , Julie Andrez","doi":"10.1039/d6qo00267f","DOIUrl":"10.1039/d6qo00267f","url":null,"abstract":"<div><div>Interest in melon-related graphitic carbon nitride (g-CN) materials has recently increased significantly due to their appealing properties as metal-free photocatalysts. Heptazine derivatives are now used in a variety of applications, including photocatalysis, organic light-emitting diodes (OLEDs), sensors, gas separation and lithium-ion batteries. However, the chemistry and functionalisation of these materials have been limited due to the difficulty of controlling the reactivity of the heptazine core. This study presents a comprehensive analysis of previously inaccessible C–C coupling reactions, including the Suzuki, Sonogashira, Stille, Kumada and Negishi reactions, which have been successfully applied to dialkylamine-substituted heptazines. These advances establish a robust platform for the derivatisation of a broader range of heptazines. Particular emphasis is placed on the Stille reaction, demonstrating the influence of aryl electronic effects on yields. The electron-withdrawing nature of the heptazine core was further confirmed by evaluating subsequent post-functionalisation (nitration, bromination, and a second Stille coupling) on selected substituted heptazines. Electrochemical (CV) and optical (UV-Vis absorption/emission) studies demonstrate a clear dependence of the electronic properties on the substituent. Overall, these findings deepen our understanding of the relationships between the structure and properties of heptazine materials, providing guidance for their targeted molecular design.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3580-3588"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148261515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Capturing CO: palladium-catalyzed, BrCF2COOK-mediated one-pot carbonylative coupling for the synthesis of oxindoles 捕集CO：钯催化，brcf2cook介导的一锅羰基偶联合成氧吲哚

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-09 DOI: 10.1039/d6qo00177g

Shivam A. Meena , Deepika Thakur , Manvi Sharma , Akhilesh K. Verma

{"title":"Capturing CO: palladium-catalyzed, BrCF2COOK-mediated one-pot carbonylative coupling for the synthesis of oxindoles","authors":"Shivam A. Meena , Deepika Thakur , Manvi Sharma , Akhilesh K. Verma","doi":"10.1039/d6qo00177g","DOIUrl":"10.1039/d6qo00177g","url":null,"abstract":"<div><div>We herein report an unprecedented palladium-catalyzed difluorocarbene transfer reaction that enables one-pot carbonylative coupling for the construction of structurally diverse and functionalized oxindole derivatives. The transformation proceeds under mild reaction conditions employing a palladium catalyst in combination with potassium bromodifluoroacetate (BrCF<sub>2</sub>CO<sub>2</sub>K), which serves as a bench-stable difluorocarbene precursor and an <em>in situ</em> carbon monoxide (CO) source. This dual functionality of BrCF<sub>2</sub>CO<sub>2</sub>K eliminates the need for external CO gas, thereby enhancing safety, cost-effectiveness, and operational simplicity. The reaction efficiently incorporates various coupling partners, including boronic acids, amines, alcohols, and alkynes, enabling the simultaneous introduction of carbonyl and functional groups into the oxindole core. The methodology exhibits a broad substrate scope, excellent functional group tolerance, and good to excellent yields, offering a versatile and practical approach for accessing valuable oxindole frameworks. Furthermore, basic hydrolysis of the reaction mixture (when methacryloyl was employed for double protection) furnished the free N–H products, which can serve as versatile intermediates for subsequent derivatization or functionalization, unlike their <em>N</em>-methyl-protected counterparts that lack such synthetic flexibility. Mechanistic insights and control experiments suggest the involvement of key Pd(<span>ii</span>) intermediates and <em>in situ</em> generated difluorocarbene species, which mediate sequential alkene insertion, carbene transfer, and carbonylation steps.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3794-3801"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147642050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Rotating magnetic field-enhanced PPh3-mediated deoxygenative C–N coupling of nitroarenes with boronic acids 旋转磁场增强pph3介导的硝基芳烃与硼酸的脱氧C-N偶联

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-29 DOI: 10.1039/d6qo00188b

Yanan Zhang , Aojie Zhang , Yue Zhang , Qing Liu , Fachao Yan , Qiang Liu , Lizhi Zhang , Maojin Tian , Zengdian Zhao , Hui Liu

{"title":"Rotating magnetic field-enhanced PPh3-mediated deoxygenative C–N coupling of nitroarenes with boronic acids","authors":"Yanan Zhang , Aojie Zhang , Yue Zhang , Qing Liu , Fachao Yan , Qiang Liu , Lizhi Zhang , Maojin Tian , Zengdian Zhao , Hui Liu","doi":"10.1039/d6qo00188b","DOIUrl":"10.1039/d6qo00188b","url":null,"abstract":"<div><div>Diarylamines are privileged motifs in pharmaceuticals, agrochemicals, and functional materials, yet their synthesis typically relies on transition-metal-catalyzed C–N couplings that require prefunctionalized anilines. We report a solvent-free electromagnetic mechanochemical protocol that enables PPh<sub>3</sub>-promoted deoxygenative C–N coupling of nitroarenes with boronic acids under a rotating magnetic field. The synergistic action of electromagnetic induction and mechanical collision activates simple triphenylphosphine to promote C–N bond formation without silanes, light, electrochemistry, or designer phosphines. Notably, bromo- and iodo-substituted substrates—often incompatible with conventional metal-catalyzed systems—remained completely intact, highlighting the exceptional halogen tolerance of this protocol. The reaction proceeds smoothly in air and without solvent, demonstrating a robust, sustainable, and magnetically driven strategy for C–N bond construction from simple and abundant feedstocks.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3674-3682"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cu(ii)-catalyzed [3 + 2] cycloaddition of enaminones and N-tosylaziridines leading to2,3-dihydropyrroles Cu（ii）催化的[3 + 2]胺酮和n - tosyziridine的环加成反应生成2,3-二氢吡咯

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-28 DOI: 10.1039/d6qo00319b

Xu Zhang , Shiru Zhao , Guo Lv , Mengxin Chen , Wenguang Li , Xuefeng Xu

引用次数: 0

Spin-selective generation of triplet alkenylcarbenes: olefin cyclopropanation through visible light photosensitization of alkenyldiazo compounds 自旋选择性生成三联体烯基羰基：烯基重偶氮化合物的可见光光敏化烯烃环丙烷化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-28 DOI: 10.1039/d6qo00337k

Sen Li , Shilin He , Yangzheng Lin , Jinbao Han , Jiating Li , Shaohui Lin , Lei Shi , Zhen Guo

引用次数: 0

α-Borylcarbene precursors: design, generation, and synthetic opportunities α-苯前体：设计、生成和合成机会

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-20 DOI: 10.1039/d6qo00368k

Ryuya Miyazaki , Kei Muto , Junichiro Yamaguchi

引用次数: 0

Post-Ugi synthesis of furo[2,3-c]isoquinolines with expanded π-conjugation displaying emission upon induced aggregation 具有扩展π共轭的呋喃[2,3-c]异喹啉类化合物的Post-Ugi合成

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-23 DOI: 10.1039/d6qo00311g

Tullio Crovetto , Lukas Biesen , Andrea Messina , Lisa Moni , Chiara Lambruschini , Bernhard Mayer , Thomas J. J. Müller , Renata Riva

引用次数: 0

Visible-light-induced acylation of active olefins by a C–C bond cleavage/Smiles rearrangement radical relay strategy via EDA complexes 通过EDA配合物的C-C键裂解/ Smiles重排自由基接力策略诱导活性烯烃的可见光酰化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-21 DOI: 10.1039/d6qo00222f

Long-Jin Zhong , Shun-Dan Li , Xiao-Han Ma , Peng-Fei Huang , Quan Zhou , Ke-Wen Tang , Chang-Hui Liu , Yu Liu

{"title":"Visible-light-induced acylation of active olefins by a C–C bond cleavage/Smiles rearrangement radical relay strategy via EDA complexes","authors":"Long-Jin Zhong , Shun-Dan Li , Xiao-Han Ma , Peng-Fei Huang , Quan Zhou , Ke-Wen Tang , Chang-Hui Liu , Yu Liu","doi":"10.1039/d6qo00222f","DOIUrl":"10.1039/d6qo00222f","url":null,"abstract":"<div><div>Photoinduced C–C bond activation of acyl oxime esters to generate aliphatic and aryl acyl radicals typically requires noble metal photocatalysts or synthetically elaborate organic dyes. In contrast, electron donor–acceptor (EDA) complex photochemistry has emerged as a powerful strategy in organic synthesis, offering operational simplicity and the potential to generate radicals <em>via</em> single electron transfer under visible-light irradiation without any photocatalysts. Herein, we report the first visible-light-induced EDA-complex-promoted acylation of 1,8-enynes through a C–C bond cleavage/Smiles rearrangement radical relay strategy. This photocatalyst- and initiator-free protocol aligns with green chemistry goals by avoiding stoichiometric oxidants, minimizing synthetic steps, and using visible light as a traceless energy source. The system tolerates both aliphatic and aryl acyl radicals simultaneously, enabling efficient access to a variety of acylated nitrogen-containing heterocycles in good to excellent yields. Notably, the transformation embodies high step-economy <em>via</em> the concurrent cleavage of four covalent bonds and formation of four new bonds in a single photochemical operation.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3602-3608"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of 8-membered tetrahydroazocines via manganese-mediated regioselective sulfonylation/cyclization of N-substituted enamides with sodium sulfinites 亚亚硫酸钠介导n -取代胺基磺化/环化合成8元四氢偶氮嘧啶

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-28 DOI: 10.1039/d6qo00401f

Ran Ding , Chuan-Hao Zhang , Jia-Qi Yuan , Pei-Li Li , Xiao-Qing Yu , Zi-Rong Li , Hui Gao

引用次数: 0

Self-aggregation and host–guest behavior of tetraureido-substituted tetranitro-azacalix[4]arenes 四金酰基取代四硝基杜鹃花[4]芳烃的自聚集和主客行为

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-06-16 Epub Date: 2026-04-28 DOI: 10.1039/d6qo00354k

Karolína Salvadori , Sabrina Pricl , Aura Tintaru , Alena Krupková , Václav Eigner , Pavel Matějka , Pavel Lhoták , Olivier Siri

{"title":"Self-aggregation and host–guest behavior of tetraureido-substituted tetranitro-azacalix[4]arenes","authors":"Karolína Salvadori , Sabrina Pricl , Aura Tintaru , Alena Krupková , Václav Eigner , Pavel Matějka , Pavel Lhoták , Olivier Siri","doi":"10.1039/d6qo00354k","DOIUrl":"10.1039/d6qo00354k","url":null,"abstract":"<div><div>The reaction of tetranitro-tetraminoazacalix[4]arene with a series of aromatic isocyanates leads to the formation of tetraureido-receptors, whose isolation was efficiently achieved (∼80% yield) by organic solvent nanofiltration when conventional chromatographic methods proved ineffective. The receptors exhibit a pronounced tendency to self-aggregate in solution, and the extent and stability of the formed assemblies are strongly modulated by the nature of the aryl substituents. A combined experimental (dilution NMR, DOSY) and theoretical investigation revealed that dimer formation arises from a cooperative interplay between π–π interactions and hydrogen bonding, with aromatic stacking providing the dominant stabilizing contribution. Molecular dynamics simulations highlight significant differences in the stability of selected dimers, rationalizing their distinct aggregation tendencies. X-ray analysis reveals that while π–π stacking remains significant even in the solid state, the ureido motifs preferentially coordinate solvent molecules. Importantly, receptor self-association does not prevent anion recognition. Even in the strongly hydrogen-bond-competitive solvent (DMSO), the receptors efficiently bind anions, exhibiting a selectivity sequence H<sub>2</sub>PO<sub>4</sub><sup>−</sup> > BzO<sup>−</sup> > AcO<sup>−</sup> ≫ Cl<sup>−</sup>, that cannot be rationalized solely by anion basicity. These findings demonstrate that tetraureido tetranitro-azacalix[4]arene architectures represent substitution-tunable supramolecular systems that combine controlled self-assembly with robust anion complexation ability.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3683-3696"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0