Organic Chemistry Frontiers最新文献_第9页

Copper-catalyzed radical transnitrilation of arylborons with dimethylmalononitrile and mechanistic insights 铜催化芳基硼与二甲基丙二腈的自由基传腈反应及其机理

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-14 DOI: 10.1039/d5qo00397k

Xiaofu Jian, Xibao Zhang, Weilong Xie

{"title":"Copper-catalyzed radical transnitrilation of arylborons with dimethylmalononitrile and mechanistic insights","authors":"Xiaofu Jian, Xibao Zhang, Weilong Xie","doi":"10.1039/d5qo00397k","DOIUrl":"https://doi.org/10.1039/d5qo00397k","url":null,"abstract":"Aromatic nitriles hold a prominent position in organic synthesis due to the unique importance of the cyanide moiety and also the diverse transformations of such groups to various functionalities. Traditional preparative routes are mainly based on Sandmeyer and Rosenmund–von Braun reactions, using toxic CuCN as a reagent. Organoborons are convenient building blocks for new chemical bond construction, and thus developing transition-metal catalytic systems for the cyanation of arylborons would provide attractive synthetic routes. Herein, we first establish the development of a mild and oxidant-free copper catalytic system for the transnitrilation of arylborons with dimethylmalononitrile (DMMN). The present system features broad scope, high functionality tolerance, scalability and practicality. Moreover, the system can be applied for the late-stage functionalization of various complex molecules. Distinct from the reported transnitrilation systems via polar mechanisms, the current copper system occurred via an unprecedent radical pathway with a Cu0/CuI catalytic cycle. The radical trapping, EPR and XPS experiments all supported the radical reaction mechanism.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827359","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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Monofluoromethylation of acyl chlorides and chloroformates employing fluorobis(phenylsulfonyl)methane. Synthesis of monofluoromethyl ketones via selective zinc-mediated reductive desulfonylation 利用含氟（苯基磺酰）甲烷对酰氯和氯甲酸盐进行单氟甲基化。选择性锌介导的还原性脱硫法合成单氟甲基酮

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-14 DOI: 10.1039/d5qo00451a

Alexander Knieb, Thomas Saal, Prabodh Rao, Xanath Ispizua-Rodriguez, G. K. Surya Prakash

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Accessing chiral sulfones with an all-carbon quaternary stereocenter via photoinduced asymmetric Truce-Smiles rearrangement and radical sulfur dioxide insertion 通过光诱导不对称 Truce-Smiles 重排和自由基二氧化硫插入，获得具有全碳四元立体中心的手性砜

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-11 DOI: 10.1039/d5qo00383k

Chenxin Wang, Wei Xiao, Jie Wu

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Palladium-Catalysed Regio- and Stereo-Controlled C-2 β- Fluorovinylation of Indoles 钯催化的区域和立体控制的吲哚的C-2 β-氟化反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-11 DOI: 10.1039/d5qo00521c

Atul K. Chaturvedi, Alastair J. J. Lennox

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Enantioselective Catalytic Urech Hydantoin Synthesis 对映选择性催化脲醛酸合成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-10 DOI: 10.1039/d5qo00378d

Wen-Ya Zheng, Zi-Qi Wang, Xing-Zi Li, Zhuo-Chen Li, Hua Wu, Abudu Rexit Abulikemu, Yu-Ping He

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Recent Advances in Repurposing Natural Enzymes for New-to-Nature Asymmetric Photobiotransformations 利用天然酶进行新自然不对称光生物转化的最新进展

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-10 DOI: 10.1039/d5qo00470e

Fulu Liu, Xichao Peng, Jinhai Yu, Xiaoqiang Huang

{"title":"Recent Advances in Repurposing Natural Enzymes for New-to-Nature Asymmetric Photobiotransformations","authors":"Fulu Liu, Xichao Peng, Jinhai Yu, Xiaoqiang Huang","doi":"10.1039/d5qo00470e","DOIUrl":"https://doi.org/10.1039/d5qo00470e","url":null,"abstract":"Photobiocatalysis, which integrates the strengths of visible-light-catalysis and enzymatic catalysis, has established itself as a pivotal tool for asymmetric synthesis. Over the past decade, several naturally occurring enzymes have been repurposed to catalyze diverse unnatural transformations that are notoriously difficult to realize using traditional methods. This Emerging Review focuses on the advancements in photobiocatalysis published from 2022 to December 2024 and also highlights earlier seminal reports related to the first demonstration. We organize this review by the coupling modes of visible-light and enzymes, including net-reduction photoenzymatic catalysis (typically) through the illumination of enzymatic electron donor-acceptor complexes, redox neutral photoenzymatic catalysis via direct-visible-light excitation of enzymes, and synergistic dual photo-/enzymatic catalysis. With each section, the discussion is categorized by the type of enzyme, emphasizing the underlying mechanistic aspects, evolutionary trajectories and representative substrate scopes. We anticipate that this review will inspire further developments and application of photobiocatalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813750","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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Direct Suzuki–Miyaura Cross-Coupling of C(sp2)–B(dan) Bonds Designed in Pursuit of Usability 为追求可用性而设计的C(sp2) -B （dan）键的直接Suzuki-Miyaura交叉耦合

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-10 DOI: 10.1039/d5qo00230c

Hiroki Andoh, Ryo Nakagawa, Tatsuya Akutagawa, Eiko Katata, Teruhisa Tsuchimoto

{"title":"Direct Suzuki–Miyaura Cross-Coupling of C(sp2)–B(dan) Bonds Designed in Pursuit of Usability","authors":"Hiroki Andoh, Ryo Nakagawa, Tatsuya Akutagawa, Eiko Katata, Teruhisa Tsuchimoto","doi":"10.1039/d5qo00230c","DOIUrl":"https://doi.org/10.1039/d5qo00230c","url":null,"abstract":"We developed practical reaction conditions and procedure for the direct Suzuki–Miyaura cross-coupling (SMCC) of C(sp2)–B(dan) bonds. Below are important notes to successfully execute the direct SMCC: 1) Dehydrated conditions that exclude as much H2O as possible are required, 2) LiOH is a base of choice, 3) dppf is a ligand of choice when using electron-deficient (hetero)aryl halides [(Het)ArX], 4) P(t-Bu)3 is a ligand of choice when using electron-rich (Het)ArX, 5) COD is a ligand of choice when using (Het)ArX with a protic functional group such as NH2 and OH. Taking heed of these notes enables the direct SMCC of the C(sp2)–B(dan) bond by a wide range of substrates with diverse functional groups, giving the following series of coupling products: Ar–Ar, Ar–HetAr, HetAr–HetAr, alkenyl–Ar, and alkenyl–alkenyl. Sequentially executing distinct types of palladium-catalyzed CCs, such as Buchwald–Hartwig CC + SMCC, Mizoroki–Heck reaction + SMCC, and Sonogashira–Hagihara CC + SMCC, allow to access complex π-conjugated molecules. The B(dan) moiety also exhibits outstanding compatibility with Wittig olefination and Sc(OTf)3-catalyzed acetal-forming reaction, enabling molecular transformations that are otherwise impracticable when using ArB(OH)2. Mechanistic studies suggested the involvement of both path A, wherein a boronate species reacts with an arylpalladium halide, and path B, wherein a boron compound reacts with an arylpalladium hydroxide, at the stage of the transmetalation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813749","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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A Metal-free, Green Strategy for Intramolecular Aminoalkoxylation of Unfunctionalized Olefins via Recyclable NIS Catalysis with Water as the Sole Byproduct 以水为唯一副产物的可循环NIS催化非功能化烯烃分子内氨基烷氧基化的无金属绿色策略

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-10 DOI: 10.1039/d5qo00535c

Hui Sun, Liyuan Zhang, Xin Wu, Bin Cui

{"title":"A Metal-free, Green Strategy for Intramolecular Aminoalkoxylation of Unfunctionalized Olefins via Recyclable NIS Catalysis with Water as the Sole Byproduct","authors":"Hui Sun, Liyuan Zhang, Xin Wu, Bin Cui","doi":"10.1039/d5qo00535c","DOIUrl":"https://doi.org/10.1039/d5qo00535c","url":null,"abstract":"A green and metal-free strategy for the synthesis of diverse structural prolinol derivatives through intramolecular aminoalkoxylation of unfunctionalized olefins in up to 96% isolated yields has been reported. This protocol used easily recyclable NIS as catalysis and accomplished in a mild reaction condition which enabled environmentally friendly alcoholic compounds as reaction solvent and alkoxyl sources. Notably, water is generated as the sole byproduct, emphasizing the green nature of the process. Experimental evidence and DFT calculations support a mechanistic pathway proceeding via aziridinium ion formation rather than through iodonium intermediates; subsequent aziridinium ion ring-opening by alcohol affords the desired products. The NIS catalyst is readily regenerated under an oxygen atmosphere, eliminating the need for transition metals or stoichiometric oxidants. This robust and scalable approach thus represents a valuable advance in the synthesis of prolinol derivatives and highlights the potential of cyclic aziridinium ion intermediates in sustainable nitrogen-heterocycle construction.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"10 1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813748","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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[2.2]Paracyclophane-substituted Quinolines by Skeletal Editing Strategies [2.2]副环蒽取代喹啉类药物的骨架编辑策略

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-09 DOI: 10.1039/d5qo00505a

Tilman Köhler, Olaf Fuhr, Stefan Bräse

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Aromaticity Switch of Borabenzene: From Aromatic when Free or Weakly Aromatic when Fused to 2D PAHs to Non-Aromatic when Fused to 3D Carboranes 硼苯的芳香性转换：从游离时的芳香或与二维多环芳烃融合时的弱芳香到与三维碳硼烷融合时的非芳香

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-09 DOI: 10.1039/d5qo00449g

Jordi Poater, Zahra Noori

{"title":"Aromaticity Switch of Borabenzene: From Aromatic when Free or Weakly Aromatic when Fused to 2D PAHs to Non-Aromatic when Fused to 3D Carboranes","authors":"Jordi Poater, Zahra Noori","doi":"10.1039/d5qo00449g","DOIUrl":"https://doi.org/10.1039/d5qo00449g","url":null,"abstract":"Free borabenzene is aromatic, but when fused with 3D aromatic carborane, it loses its aromaticity. A new series of ortho-carborane-fused boracycles has been successfully synthesized through selective intramolecular C–H borylation, with claims of forming fused 3D/2D aromatic systems. However, our quantum chemical analysis shows that while the boron cage maintains its aromatic character, the boracycle loses its aromaticity. The limited overlap between the π molecular orbitals of the planar boracycle and the n+1 molecular orbitals of the carborane hinders significant electronic delocalization between the two fused components. Our findings reveal that the peripheral σ-aromaticity of the carborane and the π-aromaticity of the boracycle are orthogonal, making a true 3D/2D aromatic system unattainable. In contrast, when the same boracycle is fused to a 2D aromatic polycyclic aromatic hydrocarbon (PAH), it retains partial aromaticity. Thus, the aromaticity of free boratabenzene is lost when fused with 3D aromatic carborane, i.e., it switches from aromatic to non-aromatic when fused to carborane or weakly aromatic when fused to PAHs.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"108 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813781","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