Organic Chemistry Frontiers最新文献_第9页

Sulfonamide Synthesis: Unlocking New Pathways with Aryl Triflates via Photocatalytic Coupling 磺胺合成：通过光催化偶联解锁芳基三氟酸酯的新途径

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-07 DOI: 10.1039/d5qo00954e

Hai Xu, Yimin Liu, Xiaoyan Zhang, Feng Zhang

{"title":"Sulfonamide Synthesis: Unlocking New Pathways with Aryl Triflates via Photocatalytic Coupling","authors":"Hai Xu, Yimin Liu, Xiaoyan Zhang, Feng Zhang","doi":"10.1039/d5qo00954e","DOIUrl":"https://doi.org/10.1039/d5qo00954e","url":null,"abstract":"Arylsulfonamides, essential scaffolds in pharmaceuticals and materials science, face synthetic sustainability challenges due to toxic reagents and transition-metal-dependent protocols. The emerging three-component coupling of aryl radicals, SO₂ surrogates, and amines offers a modular alternative; however, aryl radical generation from abundant phenolic precursors remains underexplored. Herein, we report a novel, transition-metal-free photocatalytic strategy for the modular synthesis of structurally diverse arylsulfonamides. This method overcomes longstanding limitations in aryl radical generation by utilizing NaI as a dual-functional catalyst and soft electron donor to directly activate abundant, biomass-derived aryl triflates under mild conditions (room temperature, UV light). The NaI-mediated system enables precise, orbital-oriented electron transfer, overcoming the inherent constraints of traditional SET mechanisms and achieving controlled aryl radical generation where previous methods failed. This novel activation strategy facilitates an efficient three-component cascade coupling with SO₂ surrogates (K₂S₂O₅) and a remarkably broad scope of amines, including aliphatic, aromatic, heterocyclic, and complex pharmaceutically relevant amines, delivering sulfonamide products in good to excellent yields.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"161 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792406","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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Copper-catalysed regioselective S-alkylation and C-3(H)activation of 4-hydroxydithiocoumarin and 4-hydroxy-2H-chromene-2-thione: Easy access to 4-methyl-3,4-dihydrothiopyran derivatives† 铜催化4-羟基二硫代香豆素和4-羟基- 2h -铬-2-硫酮的区域选择性s -烷基化和C-3(H)活化：易于获得4-甲基-3,4-二氢硫代吡喃衍生物†

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-06 DOI: 10.1039/d5qo00949a

Ahmad Ali, Santa Mondal, Mehak Sood, Prasad V. Bharatam, Abu Khan

{"title":"Copper-catalysed regioselective S-alkylation and C-3(H)activation of 4-hydroxydithiocoumarin and 4-hydroxy-2H-chromene-2-thione: Easy access to 4-methyl-3,4-dihydrothiopyran derivatives†","authors":"Ahmad Ali, Santa Mondal, Mehak Sood, Prasad V. Bharatam, Abu Khan","doi":"10.1039/d5qo00949a","DOIUrl":"https://doi.org/10.1039/d5qo00949a","url":null,"abstract":"An useful and expedient synthetic route for the synthesis of 4-methyl-3,4-dihydrothiopyran derivatives (3a-p & 6a-o) was accomplished from 4-hydroxydithiocoumarins/4-hydroxy-2H-chromene-2-thione and substituted vinyl ethers in the presence of 10 mol% Cu(I) iodide catalyst in toluene under reflux conditions. Notably, the reaction between 4-hydroxydithiocoumarin and ethyl vinyl sulphide (4) also provided the cyclized products (5a-e), whereas the reaction between 4-hydroxy-2H-chromene-2-thione and ethyl vinyl sulphide (4) gave only the hydrothiolation products (7a-c) under identical reaction conditions. Similarly, the reaction of 4-hydroxydithiocoumarin with phenyl vinyl ether also provided the hydrothiolation products (3q-s) instead of the expected cyclized products under similar reaction conditions. The DFT calculations has been carried out for the formation products to establish reaction mechanisms and reaction energy profiles. The present methodology involves the formation of two new C-C bonds and one C-S bond via regioselective S-alkylation and C-3 activation of 4-hydroxydithiocoumarin/4-hydroxy-2H-chromene-2-thione in a single step at the expense of one C-O/C-S bond. The current procedure possesses several positive features, such as broad substrate scope, high regioselectivity, moderate to good yields, high atom economy, mild reaction conditions, and shorter reaction time.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144787303","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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Access to benzo[e][1,3]thiazin-4-ones via PCy3-mediated annulations of benzo[c][1,2]dithiol-3-ones with iso(thio)cyanates pcy3介导苯并[c][1,2]二硫醇-3-酮与异（硫）氰酸酯环的合成[e][1,3]噻嗪-4-酮

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-05 DOI: 10.1039/d5qo01013f

Chengxiang Yi, Mingyang Zhu, Jie Ren, Weimin Zhu, Chuanjun Song, Yangang Wu

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Photocatalytic α-Nucleophilic Fluorination of α,β-Unsaturated Carbonyl Compounds α，β-不饱和羰基化合物的光催化α-亲核氟化反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-02 DOI: 10.1039/d5qo00877h

Fang Wang, Jie Gong, Jian-Ping Qu, Yan-Biao Kang

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From Nonporous to Porous: Carbazole-Integrated π-Conjugated Pillar[5]arene Crystals for Enhanced Iodine Capture 从无孔到多孔：咔唑集成π共轭柱[5]芳烃晶体增强碘捕获

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-01 DOI: 10.1039/d5qo01006c

Jin-Fa Chen, Xu-Xu Jia, Xiao-Peng Ling, Yu-Xi Yuan, Bingbing Shi, Qi Lin, Hong Yao, Tai-Bao Wei

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Theoretical Insights into the Mechanism and Selectivities of Rhodium/Amine Dual Catalysis in Alkyne-Cyclopropene Reassembly Reactions 铑/胺双催化在炔-环丙烯重排反应中的机理和选择性的理论见解

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-01 DOI: 10.1039/d5qo00898k

Guanghui Song, Keying Zhang, Huan Wang, Juan Li

{"title":"Theoretical Insights into the Mechanism and Selectivities of Rhodium/Amine Dual Catalysis in Alkyne-Cyclopropene Reassembly Reactions","authors":"Guanghui Song, Keying Zhang, Huan Wang, Juan Li","doi":"10.1039/d5qo00898k","DOIUrl":"https://doi.org/10.1039/d5qo00898k","url":null,"abstract":"Rhodium/amine dual catalysis has recently emerged as a powerful strategy for C–C bond reconstruction between cnjugated alkynes and cyclopropenes, offering new opportunities for complex molecule synthesis. In this work, we performed detailed density functional theory (DFT) investigations to elucidate the full reaction mechanism and the selectivity-determining factors underlying this cascade transformation involving cyclopropenes. Our mechanistic study reveals significant deviations from the previously proposed experimental mechanism, most notably that the reaction proceeds via a cooperative rather than a relay-type mechanism, with rhodium and amine catalysts acting synergistically throughout the catalytic cycle. ETS-NOCV analyses uncover a dual role of the Rh₂(esp)₂ complex: it assists amine-mediated alkyne activation by promoting σ-character development and through-metal delocalization, and it plays a crucial role in the cyclopropane ring-opening and water-addition steps by stabilizing transition states through substantial substrate-to-Rh charge transfer and strengthened Rh–C bonding. GRI and FMO analyses further reveal that dimethylamine electronically activates the alkyne substrate, enhancing its nucleophilicity and facilitating a more accessible reaction pathway. In addition, ligand- and amine-dependent variations in yields are well explained by ECDA and distortion–interaction analyses, which reveal that electron-rich Rh ligands and less sterically hindered amines enhance catalytic efficiency by promoting charge transfer and minimizing structural distortion in the transition state. Taken together, these findings provide valuable design principles for developing next-generation dual catalytic systems for selective and efficient C–C bond transformations.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756669","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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Modular assembly of 4-trifluoromethyl substituted 2-imino-1,3-oxathioles via cobalt(II)-based metalloradical catalysis 基于钴（II）基金属催化的4-三氟甲基取代2-亚胺-1,3-草硫唑的模块化组装

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-01 DOI: 10.1039/d5qo00989h

Chengxiao Liu, Baiquan Wang, Bin Li

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Electrophilic Intermolecular Halo-Phosphorothiolation and Phosphorothiolation-Dearomatization of Alkenes/Alkynes with N-Phosphorothiosuccinimide n-磷硫代琥珀酰亚胺的亲电分子间卤代磷硫代和磷硫代脱芳化烯烃/炔

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-01 DOI: 10.1039/d5qo00959f

Yuan Zhang, Mingyang Chen, Xu Chen, Xuesi Zhou, Yitai Fu, Xiang Liu, Hua Cao

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Anionic 5-endo-dig cyclizations: an experimental investigation of in-plane aromaticity involving a non-enolate carbanion nucleophile 阴离子5-内环化：涉及非烯醇碳离子亲核试剂的面内芳香性的实验研究

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-08-01 DOI: 10.1039/d5qo00547g

Kristina M. Nugent, Silas Q. Hintze, Pradip Maity, Salvatore D Lepore

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Beyond Energy Transfer: Ground-State Association-Driven [2+2] Cycloadditions with Indole-Fused Organophotocatalysts 超越能量转移：基态结合驱动的[2+2]环加成与吲哚-融合有机光催化剂

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-31 DOI: 10.1039/d5qo00774g

Seoyeon Kim, Byung Hak Jhun, Yunjeong Lee, Gayeon Lee, Sihyun Woo, Jaehahn Bae, Sohee Lee, Seoyeon Kim, Youngmin You, Eun Jin Cho

{"title":"Beyond Energy Transfer: Ground-State Association-Driven [2+2] Cycloadditions with Indole-Fused Organophotocatalysts","authors":"Seoyeon Kim, Byung Hak Jhun, Yunjeong Lee, Gayeon Lee, Sihyun Woo, Jaehahn Bae, Sohee Lee, Seoyeon Kim, Youngmin You, Eun Jin Cho","doi":"10.1039/d5qo00774g","DOIUrl":"https://doi.org/10.1039/d5qo00774g","url":null,"abstract":"A visible-light-driven [2+2] cycloaddition strategy with indole-fused organophotocatalysts (organoPCs) developed in our laboratory is presented, highlighting a sustainable approach with minimal solvent usage and no sacrificial reagents. Mechanistic investigations, supported by spectroscopic analyses and density functional theory (DFT) calculations, suggest that this transformation proceeds via a ground-state association mechanism rather than the more commonly proposed energy transfer pathway. Specifically, noncovalent interactions between the organoPC and a cinnamate substrate enable the formation of a [PC···substrate] complex, which, upon photoexcitation, engages in an efficient route to the triplet state that drives [2+2] cycloaddition. Structural tuning of the organoPC framework proves critical to catalytic performance, as pentacyclic architectures featuring extended π-conjugation display enhanced π–π interactions and the superior reactivity. This design principle facilitates regioselective cycloadditions across a broad range of functionalized cinnamate derivatives, highlighting the versatility and atom economy achievable under visible-light irradiation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"143 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0