Organic Chemistry Frontiers最新文献_第10页

Electrochemical Alkene Radical Cation-Enabled 1,2-Aryl Migration of Allylic Alcohols: Synthesis of α-Quaternary Ketones 烯丙醇电化学自由基阳离子使1,2-芳基迁移：α-季酮的合成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-15 DOI: 10.1039/d6qo01142j

Peng Chen,Xiao-Qing Xie,Jiang Bai,Ruchun Yang,Lin Lu,Xian-Rong Song,Mu-Jia Luo,Qiang Xiao

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Eschenmoser's salts: from design to applications in organic synthesis Eschenmoser的盐：从设计到有机合成的应用

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Organic Chemistry Frontiers Pub Date : 2026-09-15 DOI: 10.1039/d6qo00713a

Margherita Miele,Eisuke I. Comas Iwasita,Andrea D'Annibale,Andrés R. Alcántara,Laura Castoldi,Vittorio Pace

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One-pot divergent synthesis of 5-arylmethyl oxazoles and polyacenes from propargylic amides and arynes 丙炔酰胺和芳烃一锅发散合成5-芳基甲基恶唑和聚芳烯

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-14 DOI: 10.1039/d6qo01223j

Alan Yannic Rolf Werling,Yun Yang,Christopher Raymond Jones

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Visible-light-promoted Multicomponent Reaction of Amines, Carbon disulfide and Benzodithiol-3-ones 可见光促进胺、二硫化碳和苯二噻吩-3-酮的多组分反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-14 DOI: 10.1039/d6qo01080f

Shanhong Yang,Huizhi Hu,Baitao Zhou,Xiaobing Liu,Yao Zhou,Shengzhou Jin,Guodong Yin

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Electron-Donor-Switched Divergent Synthesis of Biaryl Amides and Phenanthridin-6(5H)-ones from 2-Iodobenzanilides 以2-碘苯并苯胺为原料，电子给体开关发散合成联芳基酰胺和菲咯啶-6(5H)-酮

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-14 DOI: 10.1039/d6qo01095d

Kun-Quan Chen,You-Qin Liu,Qiang Liu,You-Feng Han,Xiang-Yu Chen

{"title":"Electron-Donor-Switched Divergent Synthesis of Biaryl Amides and Phenanthridin-6(5H)-ones from 2-Iodobenzanilides","authors":"Kun-Quan Chen,You-Qin Liu,Qiang Liu,You-Feng Han,Xiang-Yu Chen","doi":"10.1039/d6qo01095d","DOIUrl":"https://doi.org/10.1039/d6qo01095d","url":null,"abstract":"Divergent synthesis from ortho-halogenated benzanilides provides rapid access to structurally distinct scaffolds, yet selectivity control under mild, catalyst-free conditions remains challenging. Herein, we report a charge transfer complex enabled divergent transformation of 2-iodobenzanilides, in which a simple switch of the electron donor dictates the product outcome: TMEDA delivers biaryl amides through ipso-spirocyclization and C-N bond cleavage, whereas tBuOK affords phenanthridin-6(5H)-ones via orthoaddition and oxidative rearomatization.Biaryls and biaryl-fused heterocyclic scaffolds are ubiquitous structural motifs in pharmaceuticals, natural products, and functional materials (Figure 1A). 1 The broad utility of these frameworks has stimulated sustained interest in the development of efficient and selective methods for their construction. 2 Among the various approaches reported to date, radical reactions of ortho-halogenated benzanilides have emerged as a particularly versatile platform, as the same class of precursors can, in principle, deliver both scaffolds through divergent cyclization modes of the aryl radical intermediate. 3 Historically, intramolecular ortho-addition has been exploited extensively for the synthesis of phenanthridinones, and a wide array of transition-metal-catalyzed and radical protocols have been established along this line. 4 In contrast, ipso-additionwhich would lead, upon amide migration or fragmentation, to unfused biaryl products-is generally disfavored and has proven considerably more challenging to realize. 5 An advance in this direction was reported by Butterworth and Greaney, who demonstrated that amide substrates bearing a blocking","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148957884","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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Manganese-Catalyzed C–O Bond Scission Triggered by C–H Oxidation in 1-Arylisochromans 1-芳基等色体C-H氧化引发的锰催化C-O键断裂

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-11 DOI: 10.1039/d6qo00999a

Jimei Zhou,Xiaoxu Wang,Ning Ma,Jiangping Cao,Juanjuan Wei,Sam de Visser,Jianliang Xiao,Chaoqun Li

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Isolable, Highly Strained Silabicyclic Bridgehead Alkenes 可分离的高应变硅环桥头堡烯烃

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-10 DOI: 10.1039/d6qo01165a

Desheng Chen,Huayu Liang,Cheng Xu,Zhuofeng Ke,Yaofeng Chen

{"title":"Isolable, Highly Strained Silabicyclic Bridgehead Alkenes","authors":"Desheng Chen,Huayu Liang,Cheng Xu,Zhuofeng Ke,Yaofeng Chen","doi":"10.1039/d6qo01165a","DOIUrl":"https://doi.org/10.1039/d6qo01165a","url":null,"abstract":"Bredt's rule has long defined the limits of bridgehead alkenes, and the synthesis of highly strained members of this class remains a formidable challenge. Herein, we report the synthesis, structure, and reactivity of a series of siliconcontaining bridgehead alkenes-silabicyclo[3.1.0]alk-5-enes and silabicyclo[4.1.0]alk-6-enes-which are highly strained yet stable and isolable. The title compounds are prepared via a salt-elimination strategy from a potassium silylene precursor and ω-bromoalkynes (RCCCH2(CH2)nCH2Br) (n = 1, 2). This process involves naphthalene dissociation to generate the key silylene intermediate, followed by its intramolecular cyclization with the alkyne group. Single-crystal X-ray diffraction and DFT calculations reveal pronounced pyramidalization and twisting of the C=C bond. Despite this severe distortion, these compounds are thermally robust due to π→σ* stabilization between the C=C bond and adjacent Si-C σ* orbitals. Silabicyclo[3.1.0]alk-5-ene displays versatile reactivity, undergoing ring-opening reactions with a wide range of E-H bonds (E = O, N, S, Si, etc.) and ringexpansion reactions with unsaturated compounds such as isocyanides, pyridazine, CO₂, and diphenylcyclopropenone under mild conditions, providing facile access to diverse organosilicon frameworks. Furthermore, the mechanism of the CO₂ insertion reaction was elucidated by DFT calculations, revealing a concerted asynchronous pathway with an energy barrier of 24.1 kcal/mol.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"145 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915250","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

Mechanistic insights into solvent-controlled chemodivergent Rhcatalyzed C-H functionalization of N-methoxybenzamide n -甲氧基苯甲酰胺溶剂控制化学发散催化C-H功能化的机理研究

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-10 DOI: 10.1039/d6qo00917d

Yang Wang,Yan-Kun Cui,Lujun Zhang

{"title":"Mechanistic insights into solvent-controlled chemodivergent Rhcatalyzed C-H functionalization of N-methoxybenzamide","authors":"Yang Wang,Yan-Kun Cui,Lujun Zhang","doi":"10.1039/d6qo00917d","DOIUrl":"https://doi.org/10.1039/d6qo00917d","url":null,"abstract":"Solvent-mediated chemoselectivity control offers a straightforward and powerful strategy for accessing structurally diverse products from identical starting materials in transition-metal-catalyzed C-H functionalization reactions. However, the mechanistic basis for solvent-switchable chemodivergent reactions remains largely unclear. Herein, we report a comprehensive computational investigation that elucidates the reaction mechanism, origin of stereoselectivity, and the fundamental driving force behind solvent-regulated chemoselectivity. Our calculations reveal that a low-polarity solvent ( i PrCN) favors the formation of (Z)-monofluoroalkenyl isoindolinone, whereas a highly polar solvent (MeOH) leads to the alkynyl isoindolinone product. In MeOH, kinetically favorable inner-oriented fluoride elimination triggers a second β-F extrusion to release the alkynyl isoindolinone. By contrast, outer-oriented fluoride elimination dominates in i PrCN, followed by protonolysis to furnish the monofluoroalkenyl product. The alkyne insertion step determines both the rateand stereoselectivity, preferentially generating the R-configured isomer as the major product. Steric buried volume (%VBur) and activation strain model (ASM) analyses collectively confirm that severe steric congestion and elevated distortion energy destabilize the minor stereoisomeric transition state. Electrostatic potential surface analysis further reveals the origin of solvent-controlled chemoselectivity: highly polar MeOH stabilizes charge-separated, high-dipole zwitterionic transition states leading to alkynyl product, whereas low-polarity i PrCN destabilizes such ionic transition states, rendering the low-dipole pathway leading to monofluoroalkenyl isoindolinone kinetically advantageous. This work establishes a quantitative mechanistic framework for solvent-tunable chemodivergent asymmetric C-H activation and provides rational guidelines for designing solvent-switchable synthetic routes to diverse molecules.2","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"51 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148908842","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

Visible-light-mediated selective α-polyfluoroarylation and alkenylation of phenol- and thiophenol-derived aryl alkyl ethers 可见光介导的选择性α-多氟芳基烷基醚和苯酚及噻吩衍生芳基烷基醚的烷基化

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-09 DOI: 10.1039/d6qo01031h

Ting Zhang,Siyuan Xiong,Delin Wu,Tianbao Liu,Shuguang Chen,Yongjia Shang,Hao Wu

引用次数: 0

Mechanistic Insights into a Four-Component Catellani Reaction: How Self-Inhibition Governs Electrophile Ordering 四组分Catellani反应的机理：自抑制如何支配亲电试剂的排序

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-09 DOI: 10.1039/d6qo01169a

Bo Xiao,Chengxi Yang,Jinning Yin,Tian-Yu Sun

{"title":"Mechanistic Insights into a Four-Component Catellani Reaction: How Self-Inhibition Governs Electrophile Ordering","authors":"Bo Xiao,Chengxi Yang,Jinning Yin,Tian-Yu Sun","doi":"10.1039/d6qo01169a","DOIUrl":"https://doi.org/10.1039/d6qo01169a","url":null,"abstract":"Multicomponent coupling is a powerful strategy to rapidly build complex molecules, yet its broader application is often limited by poor chemoselectivity arising from competing cross-couplings among multiple substrates. Luan and co-workers recently disclosed a four-component Catellani reaction that enables sequence-controlled ortho difunctionalization of aryl iodides, in which benzoic anhydride and benzyl bromide undergo oxidative addition in a defined order. However, the mechanistic origin of this electrophile ordering has remained unclear. Herein, we employ density functional theory calculations to elucidate the factors governing this chemoselectivity. We identify benzoic anhydride as a self-inhibitory electrophile: its initial incorporation installs a benzoyl group that preferentially suppresses further reaction through the anhydride pathway, thereby shifting the relative selectivity of the second oxidative addition toward benzyl bromide. In addition, the anhydride pathway exhibits a markedly stronger dependence on electronic substituent effects than the benzyl bromide pathway. These mechanistic insights clarify the origin of electrophile ordering in this challenging four-component process and provide a theoretical foundation for future electrophile selection in multicomponent Pd/NBE catalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148908843","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