Journal of Organic Chemistry最新文献_第10页

Metal-Free C–H Heterofunctionalization of Naphthoquinone via Unprecedented C–N Bond Formation and Cleavage Using Imidazole 通过史无前例的C-N键形成和咪唑裂解萘醌的无金属C-H杂官能化

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-06 DOI: 10.1021/acs.joc.4c03162

Adarsh Krishna T.P, Pandaram Sakthivel, Laxman Kota, Kumaresan Kalainilavan, Kathiravan Asokan, Andivelu Ilangovan

引用次数: 0

Chalcogen Bonding with Telluronium Cations: toward Selective Population of Tellurium σ-Holes by Lewis Bases. 硫与碲离子成键：路易斯碱对碲σ-空穴的选择居群。

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-06 DOI: 10.1021/acs.joc.5c00744

Loic Groslambert, Yann Cornaton, Patrick Pale, Matej Ditte, Alexandre Tkatchenko, Jean-Pierre Djukic, Victor Mamane

{"title":"Chalcogen Bonding with Telluronium Cations: toward Selective Population of Tellurium σ-Holes by Lewis Bases.","authors":"Loic Groslambert, Yann Cornaton, Patrick Pale, Matej Ditte, Alexandre Tkatchenko, Jean-Pierre Djukic, Victor Mamane","doi":"10.1021/acs.joc.5c00744","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00744","url":null,"abstract":"The reaction of tris[3,5-bis(trifluoromethyl)phenyl]telluronium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF-) salt with phosphine oxides OPR3 in 1,2-dichloroethane is exothermic and leads to the population of the three Te σ-holes. Quite unprecedented, careful adjustment of the stoichiometry of reagents allowed the selective crystallization of the Lewis adducts containing one, two, or three Te-bonded OPR3, according to X-ray diffraction. 1H and 19F Diffusion-ordered NMR spectroscopy-monitored titrations of the telluronium salt by OPPh3 reveal the growth of the hydrodynamic volume of the various cationic adducts, alongside a unique behavior of the BArF- counterion that suggests its aggregation at high cationic molecular sizes. Isotherm titration calorimetry experiments show that the association equilibrium constants of OPR3 binding to Te σ-holes follow the order Ka1 > Ka2 > Ka3, with respective values decreasing by 1 up to 2 orders of magnitude as the σ-holes are populated. Analysis of Te-O bonding by DFT methods confirms their dominant Coulombic character. The minor covalent character is nonetheless required to ensure telluronium-ligand cohesion. DFT calculations of the association thermochemistry raise the tangible contribution of ion \"pairs\" to the association enthalpy as a major issue for modeling: the allegedly \"non-coordinating\" BArF- taking part in elusive multipolar ion-pairs is far from being an irrelevant thermochemical contributor.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

One-Step Introduction of Nitrogen-Containing Functional Groups onto Aryl Methyl Ketones: Synthesis of α-Iminoamidines with Tunable Biorelevant Properties 芳基甲基酮一步引入含氮官能团：具有可调生物相关性质的α-亚胺胺的合成

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c00224

Milan S. Nešić, Milica D. Nešić, Dragan B. Zlatković, Marko V. Rodić, Matic Lozinšek, Niko S. Radulović

引用次数: 0

DABCO-Catalyzed Nucleophilic Aromatic Substitution and Its Use in Improving the Synthesis of O2-Benzylcytosines as Substrates of CLIP-Tag dabco催化的亲核芳香取代及其在改进作为CLIP-Tag底物的o2 -苄基胞嘧啶合成中的应用

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.4c02920

Kevin N. Little, Gideon Ofosu Addai, Colin C. Stanwood, Christelle F. T. Bucag, Xinsong Lin, Banghao Chen, A. Carl Whittington, Lei Zhu

引用次数: 0

Visible Light-Induced Radical-Cascade Difluoroalkylation/Cyclization of Unsaturated Aldehyde Hydrazones for the Synthesis of Difluoroalkylated Dihydropyrazoles and Tetrahydropyridazines 可见光诱导的不饱和醛腙自由基级联二氟烷基化/环化合成二氟烷基化二氢吡唑和四氢吡嗪

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c00708

Hui Chen, Kaifa Zhang, Kun Xia, Yu Li, Ziwei Shan, Shuangming Zhang, Yonghong Zhang, Ablimit Abdukader

引用次数: 0

Synthesis of SeCF₃-Substituted Oxazines and Oxazolines through Electrophilic Trifluoromethylselenolation Cyclization of Propargylic Amides. 丙炔酰胺亲电三氟甲基硒化环化合成secf3取代的恶嗪和恶唑啉。

IF 3.3 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c00930

Jia Wang, Jia-Qi Niu, Jia-Cheng Li, Lixia Liu, Xuefang Shang, Ping-Xin Zhou, Shujun Chao

引用次数: 0

Visible-Light Photoredox-Catalyzed Carboxylation of Benzylic C(sp3)–O Bonds in Ethers with CO2 可见光光氧化催化乙醚中苯基C(sp3) -O键与CO2的羧化反应

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c01091

Jing-Wei Yang, Chuan-Kun Ran, Wen-Jing Zhu, Yi Jiang, Si-Shun Yan, Jian-Heng Ye, Da-Gang Yu

{"title":"Visible-Light Photoredox-Catalyzed Carboxylation of Benzylic C(sp3)–O Bonds in Ethers with CO2","authors":"Jing-Wei Yang, Chuan-Kun Ran, Wen-Jing Zhu, Yi Jiang, Si-Shun Yan, Jian-Heng Ye, Da-Gang Yu","doi":"10.1021/acs.joc.5c01091","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01091","url":null,"abstract":"Although significant progress has been made in achieving site-selective C–O bond functionalization in specific substrates, the selective cleavage and functionalization of C(sp3)–O bonds in ethers remain a fundamental challenge in synthetic chemistry. Herein, we present an efficient carboxylation method via the photoredox-catalyzed cleavage of benzylic C(sp3)–O bonds in ethers with carbon dioxide (CO2). Diverse primary, secondary, and tertiary benzyl ethers undergo selective carboxylation with CO2 to generate valuable aryl acetic acids, including several drug molecules. This photocatalyzed carboxylation reaction is operationally simple to implement and versatile for various benzylic ethers, exhibiting favorable compatibility with diverse functional groups. Mechanistic studies indicate that the single electron transfer (SET) reduction of ethers might be the key to generating a highly reactive radical anion intermediate, which could undergo C–O bond cleavage and another SET reduction process to generate carbanions for reaction with CO2.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Base-Promoted Iridium-Catalyzed Deuteration and C–H Bond Activation of N-Heterocycles 碱基促进的铱催化n -杂环的氘化和C-H键活化

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c00174

Ben J. Tickner, Claire Condon, Victoria Annis, Richard J. Gammons, Adrian C. Whitwood, Simon B. Duckett

{"title":"Base-Promoted Iridium-Catalyzed Deuteration and C–H Bond Activation of N-Heterocycles","authors":"Ben J. Tickner, Claire Condon, Victoria Annis, Richard J. Gammons, Adrian C. Whitwood, Simon B. Duckett","doi":"10.1021/acs.joc.5c00174","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00174","url":null,"abstract":"Hydrogen isotope exchange (HIE) of N-heterocycles is highly important in synthesis, where it is often used to prepare probes suitable for pharmaceutical studies. In this work, we show that pharmaceuticals such as anastrozole, trimethoprim, and bisacodyl can be easily deuterated in up to 84–95%, with high site selectivity using an [IrCl(COD)(IMes)]/H2/NaOMe/methanol-d4 derived catalytic system. We studied in detail the deuteration of quinoxaline using NMR spectroscopy, mass spectrometry, and X-ray crystallography and characterized a range of C–H bond activated products that include [Ir(H)2(quinoxaline)(IMes)(κ2-μ2-C,N-quinoaxline)2Ir(H)2(quinoxaline)(IMes)]; [Ir(H)2(quinoxaline)(IMes)(κ2-μ2-C,N-quinoxaline)2Ir(Cl)(H)(quinoxaline)(IMes)]; [Ir(H)2(IMes)(κ2-μ2-C,N-quinoxaline)2Ir(H)2(IMes)]; and [Ir(H)2(IMes)(κ2-μ2-C,N-quinoxaline)2(μ2–H)Ir(H)(quinoxaline)(IMes)]. Reaction scope is demonstrated by the examination of 17 structurally diverse substrates, with functional groups spanning pyridines, quinoxalines, quinolines, purine/xanthines, triazoles, and pyrimidines. Four analogous C–H-bond-activated X-ray structures were obtained for the additional substrates. Catalytic turnover was found to dramatically increase upon the addition of NaOMe and is linked to a demonstrated role for trihydride species [Ir(H)3(COD)(IMes)] in the HIE process, with the reactive fragment {IrH(IMes)} implicated in the formation of catalytically competent dinuclear C–H bond activation products.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Synthesis of Isoquinoline N-Oxides via Hypervalent Iodine-Mediated Oxidative Cyclization of Ketoximes with Alkenes 高价碘介导酮肟与烯烃氧化环化合成异喹啉n -氧化物

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c00488

Aurapat Ngamnithiporn, Padon Chuentragool, Supakarn Punnita, Wachirawit Thitseesaeng, Teesuda Sirichai, Shinji Harada, Tetsuhiro Nemoto, Poonsakdi Ploypradith, Somsak Ruchirawat

引用次数: 0

Rh(III)-Catalyzed Fabrication of [4,3,1]-Bridged Azaheterocycles using Quinone Monoacetals Rh（III）催化醌单缩醛合成[4,3,1]-桥接氮杂环

IF 4.354 2区化学

Journal of Organic Chemistry Pub Date : 2025-06-05 DOI: 10.1021/acs.joc.5c00392

Sushma Naharwal, Narendra Dinkar Kharat, Siva S. Panda, Kiran Bajaj, Alokananda Chanda, Sanjay K. Mandal, Rajeev Sakhuja

引用次数: 0