Organic Chemistry Frontiers最新文献_第9页

Modular access to bicyclo[1.1.1]pentyl alkylamines enabled by dual photoredox and tether-tunable distonic radical anion catalysis 双光氧化还原和系链可调双离子自由基阴离子催化实现双环[1.1.1]戊基烷基胺的模块化获取

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00879h

Chao Tian,Lei Shi

{"title":"Modular access to bicyclo[1.1.1]pentyl alkylamines enabled by dual photoredox and tether-tunable distonic radical anion catalysis","authors":"Chao Tian,Lei Shi","doi":"10.1039/d6qo00879h","DOIUrl":"https://doi.org/10.1039/d6qo00879h","url":null,"abstract":"Bicyclo[1.1.1]pentane (BCP) motifs are valuable three-dimensional bioisosteres of para-disubstituted benzenes and the tert-butyl group, but their incorporation into drug candidates is hampered by a lack of concise and modular syntheses. Here we report a dual photoredox and tether-tunable distonic radical anion (TDRA) catalyzed multicomponent difunctionalization of [1.1.1]propellane with alkyl carboxylic acids and imines, delivering diverse BCP alkylamines in one-pot operations. This mild, redox-neutral transformation accommodates primary, secondary, and tertiary carboxylic acids, as well as a broad range of acyclic aromatic imines and a representative N-sulfinylamine. Photoredox-induced single-electron oxidation of catalytic phthalate salts generates TDRAs, which then engage in polarity-matched proton-coupled electron transfer (PCET) with the O–H bond of carboxylic acids to forge C-centered radicals. This mechanistic rationale, wherein the TDRA acts as a key hydrogen-atom abstractor in a redox-neutral radical relay, is supported by radical trapping and radical clock experiments, while the initial photoinduced electron-transfer step is corroborated by Stern–Volmer luminescence quenching studies. The synthetic utility and sustainability of this dual catalytic system are further demonstrated by gram-scale reactions, late-stage functionalization of complex natural products and pharmaceuticals, favorable green chemistry metrics, and biocompatibility with biologically relevant macromolecules. This modular platform thus provides expedient access to functionalized BCP-containing bioisosteres, constituting a practical and general strategy for incorporating sp3-rich scaffolds into drug discovery.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973545","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

Rigid all-hydrocarbon molecular bows: synthesis, structures, strain distribution and photophysical properties 刚性全烃分子弓：合成、结构、应变分布和光物理性质

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00758a

Xiaolin Chen,Bo Zou,Wenrui Yang,Taoxing Yu,Qingyun Jiang,Cong Liu,Jieqing Huang,Haoran Liu,Hua-Wei Jiang

{"title":"Rigid all-hydrocarbon molecular bows: synthesis, structures, strain distribution and photophysical properties","authors":"Xiaolin Chen,Bo Zou,Wenrui Yang,Taoxing Yu,Qingyun Jiang,Cong Liu,Jieqing Huang,Haoran Liu,Hua-Wei Jiang","doi":"10.1039/d6qo00758a","DOIUrl":"https://doi.org/10.1039/d6qo00758a","url":null,"abstract":"Fully rigid molecular bows are hard to construct due to high ring strain. Herein, we report the synthesis, structures, strain distribution, and photophysical properties of fully rigid, all-hydrocarbon molecular bows, in which bowstring and bow-limbs are entirely phenylene units linked by bridging carbon atoms. A modular platinum-mediated one-pot cyclization of a carbon-bridged biphenyl diboronate with either 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene or 4,4′-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,1′-biphenyl affords Medium (p-terphenyl limb), Large (p-quaterphenyl limb), and Small (biphenyl limb) bows. Single-crystal X-ray diffraction reveals bow-like conformation with systematic cavity expansion. As the bow size increases, the bending angles of the bowstring phenyl rings decrease sharply, whereas their torsion angles increase dramatically; concurrently, bending of the proximal limb decreases while that of the central limb increases. Visualized strain distribution shows that in the Small bows, strain is highly localized at the C–C bonds connecting the biphenyl units to the bridging carbon atoms. In contrast, for the Medium and Large bows, the strain diffuses along the longer bow-limb, with much less strain imposed on the bowstring. All these molecular bows exhibit bright dual-state emission. This work establishes a new paradigm for fully rigid molecular bows and provides deep insights into their structural characteristics and strain distribution.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973546","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

Cascade migration-aryloxylation of 2-alkyl/alkenyl quinoline -oxides with phenols: practical synthesis of 2,3-disubstituted quinolines 2-烷基/烯基喹啉氧化物与酚的级联迁移-芳基化：2,3-二取代喹啉的实际合成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00735j

Fenlian Xu,Tong Han,Hua Xiao,Xinqiao Nie,Yiyan Hong,Dong Wang

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Enantioselective synthesis of axially chiral chromene- and quinoline-based fused heterocyclic biaryls asymmetric Suzuki–Miyaura coupling 轴手性铬基和喹啉基融合杂环双芳基不对称Suzuki-Miyaura偶联的对映选择性合成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00743k

Siming Liang,Minghui Li,Can Liu,Xinyu Gao,Shaobin Chen,Changwei Yu,Lihong Yu,Wenhao Wu

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Iron-mediated [5 + 2]/[6 + 2] cycloadditions of photogenerated siloxyketenes: access to medium-sized diazaheterocycles 铁介导的[5 + 2]/[6 + 2]光生硅氧酮的环加成：获得中等重氮杂环

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00807k

Xiangjun Ma,Bo Li,Yuting Chen,Ting Song,Quannan Wang,Wei-Ping Deng

引用次数: 0

Visible-light-induced DABCO-mediated cascade cyclization of aryl alkenes, aldehydes, and TBN: a convenient, green synthesis of 5-hydroxyisoxazole 可见光诱导的dabco介导的芳基烯烃、醛和TBN级联环化：一种方便、绿色的5-羟基异恶唑合成方法

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00747c

Meifang Wang,Hemin Rong,Mahmut Adila,Ping Jiang,Hairong Ma,Keyume Ablajan

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Catalytic alkoxysilylation of (hetero)aryl bromides with -butyl alkoxysilyldiazenes （杂）芳基溴与-丁基烷氧基硅基二氮的催化烷氧基硅化反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-16 DOI: 10.1039/d6qo00844e

Lamine Saadi,Clément Chauvier

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Copper-Catalyzed Selective 1,4-Allylboration/Silylcinnamylation of 2-Trifluoromethyl-1,3-Enynes for Synthesis of Multifunctional Tetrasubstituted Allenes 铜催化2-三氟甲基-1,3-炔选择性1,4-烯丙基硼化/硅基肉桂化合成多功能四取代烯烯

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-15 DOI: 10.1039/d6qo01186a

Guangyu Li,Tao Zhu,Jinhua Wan,Lechi Zhang,Cheng Fu,Chongcai Jiang,Yuzhe Lu,Xiaotao Zhu,Jiuzhong Huang

{"title":"Copper-Catalyzed Selective 1,4-Allylboration/Silylcinnamylation of 2-Trifluoromethyl-1,3-Enynes for Synthesis of Multifunctional Tetrasubstituted Allenes","authors":"Guangyu Li,Tao Zhu,Jinhua Wan,Lechi Zhang,Cheng Fu,Chongcai Jiang,Yuzhe Lu,Xiaotao Zhu,Jiuzhong Huang","doi":"10.1039/d6qo01186a","DOIUrl":"https://doi.org/10.1039/d6qo01186a","url":null,"abstract":"A copper-catalyzed three-component 1,4-allylboration/silylcinnamylation (simultaneous installation of silyl and cinnamyl groups) of 2-trifluoromethyl-1,3-enynes with allyl halogen and B2pin2 or BpinSiMe2Ph is reported. This method provides a direct and regioselective route to tetrasubstituted allenes bearing a trifluoromethyl group, boryl/silyl and allyl/cinnamyl units in a single step. This transformation proceeds with exclusive chemo- and regi-oselectivity, tolerating an extensive library of aryl, heteroaryl, alkenyl and functionalized substrates, including complex natural product-derived skeletons. Practical synthetic utility is demonstrated via gram-scale preparation and diversified downstream derivatization: conjugated dienes, cyclic frameworks, diverse boron derivatives, among others. Mechanistic investigations validate the trifluoromethyl substituent acts as an indispensable di-recting group, which enables selective migratory insertion of borylcopper or silylcopper species into the alkene C=C bond rather than the alkyne C≡C triple bond; control experiments exclude any radical-mediated catalytic cy-cle. This protocol establishes a straightforward platform for assembling structurally diverse allyl-substituted allene building blocks for drug discovery and synthetic methodology.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148964451","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

A Unified Strategy for α-Alkoxyalkyl Radical Generation via Pinacol Boronic Ester Precursors 甲萘酚硼酯前体生成α-烷氧烷基自由基的统一策略

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-15 DOI: 10.1039/d6qo01025c

Emy André-Joyaux,Lise Benoist,Agathe Fayolle,Fabrice Dénès,Philippe Renaud

引用次数: 0

Brønsted Base-Regulated Oxidation Pathways of NHPI in Electrochemical PINO Generation Brønsted碱基调控NHPI在电化学生成PINO中的氧化途径

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-09-15 DOI: 10.1039/d6qo01122e

Wen-Yue Lin,Xiao-Hui Liu,Jing-Zhou Wang,Guo-Sheng Wang,Jing-Ru Feng,Ya-Song Lin,Hai-Yang Yu,Can Xue,Xiantai Zhou

{"title":"Brønsted Base-Regulated Oxidation Pathways of NHPI in Electrochemical PINO Generation","authors":"Wen-Yue Lin,Xiao-Hui Liu,Jing-Zhou Wang,Guo-Sheng Wang,Jing-Ru Feng,Ya-Song Lin,Hai-Yang Yu,Can Xue,Xiantai Zhou","doi":"10.1039/d6qo01122e","DOIUrl":"https://doi.org/10.1039/d6qo01122e","url":null,"abstract":"The phthalimide N-oxyl radical (PINO), generated from N-hydroxyphthalimide (NHPI), is a versatile hydrogen-atom-transfer mediator for the selective oxidation of benzylic and aliphatic C-H bonds. Efficient electrochemical generation of PINO is therefore critical to the performance of NHPI-mediated oxidation, and Brønsted bases are commonly employed to facilitate this process. Their function, however, has generally been considered primarily in terms of proton acceptance. Here, we demonstrate that base identity also controls the locus of the initial anodic electron-removal event within the preassociated NHPI-base assembly, thereby directing PINO formation through mechanistically distinct pathways. Pyridine favors predominantly NHPI-centered oxidation followed by proton transfer in a sequential ET/PT process, whereas 4-aminopyridine exhibits substantial base-centered oxidation character and subsequently activates NHPI through hydrogen-atom transfer in a stepwise ET/HAT sequence. This mechanistic divergence is substantiated by cyclic voltammetry, in situ electrochemical EPR spectroscopy, 1 H NMR titration studies, DFT calculations, Arrhenius analysis, and apparent isotope-effect measurements. Relative to the 4-aminopyridine system, the pyridine-mediated pathway affords greater steady-state PINO accumulation, enhanced electrochemical reversibility, a lower apparent activation energy, and consistently higher conversions across representative benzylic and aliphatic C-H substrates. These findings establish base-controlled localization of the initial electron-transfer event as a decisive mechanistic parameter governing productive NHPI electrocatalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148964450","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