Organic Chemistry Frontiers最新文献

{"title":"Cationic and Homoleptic Copper(I)–Thiazol-2-ylidenes: Highly Reactive Thiazole N-Heterocyclic Carbenes σ-Lewis Acid Catalysts","authors":"Ruihong Wang, Jin Zhang, Hang Yang, Yawei Zhu, Yan Guo, Xiaoxia Han, Roman Szostak, Michal Szostak","doi":"10.1039/d5qo00772k","DOIUrl":"https://doi.org/10.1039/d5qo00772k","url":null,"abstract":"Air- and moisture-stable cationic homoleptic Cu(I) thiazol-2-ylidene complexes are developed as highly efficient σ-Lewis acid catalysts, outperforming imidazol-2-ylidenes in the alkynylation of ketones without requiring stoichiometric Cu-acetylides. These complexes exhibit exceptional operational simplicity and robustness, enabling key C–C bond formation. Structural insights and DFT studies highlight their enhanced reactivity and stability. With their superior performance and practicality, thiazol-2-ylidenes represent a promising class of catalysts for sustainable organic synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"93 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747599","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}

{"title":"Asymmetric Biomimetic Aldol Reaction of Glycinate with Aliphatic Aldehydes for Efficient Synthesis of Chiral β-Hydroxy-α-Amino Acid Esters","authors":"Tao Liu, Dong Ma, Mingming Lu, Ting Ma, Siqi Liu, Guoqing Zhao, Baoguo Zhao","doi":"10.1039/d5qo00653h","DOIUrl":"https://doi.org/10.1039/d5qo00653h","url":null,"abstract":"In biological systems, enzyme catalyzed processes are efficient and environmentally friendly ways for the transformations of various substances. Biomimetic processes can provide straight forward strategies for the synthesis of target molecules. Asymmetric biomimetic aldol reaction of glycinate is a highly efficient method for the synthesis of chemically and biologically important chiral β-hydroxy-α-amino acid esters. Herein, we developed an asymmetric aldol reaction of glycinate with aliphatic aldehydes using chiral N-quaternized pyridoxal as catalyst, affording a variety of chiral β-hydroxy-α-amino acid esters in 20–91% yields, with up to > 20:1 dr and up to 99% ee.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"97 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719487","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}

{"title":"Transition-Metal-Free [3+2] Cycloaddition to Access Tetrazoles: Non-radical Application of Arylazo Sulfones","authors":"Yulei Zhao, Ruiqing Wang, Xinyu Zong, Wenyi Chen, Xintian Zhang, Minghui Zhang","doi":"10.1039/d5qo00840a","DOIUrl":"https://doi.org/10.1039/d5qo00840a","url":null,"abstract":"A transition-metal-free [3+2] cycloaddition between arylazo sulfones and diazo compounds is reported. Notably, arylazo sulfones demonstrate distinct reactivity characteristics; in contrast, other common azo compounds and aryldiazonium salts prove ineffective under this transition-metal-free conditions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719438","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}

{"title":"Tunable thiofumarate stereoselective cycloadditions via aminomefloquine catalysis†","authors":"Radosław Suchanek, Michał Błauciak, Anna Spyszkiewicz, Błażej Dziuk, Przemysław J. Boratyński, Rafał Szabla and Rafał Kowalczyk","doi":"10.1039/D5QO01014D","DOIUrl":"10.1039/D5QO01014D","url":null,"abstract":"<p >Norcamphane is a bicyclic, lipophilic motif present in widely used drugs. It also serves as an adamantane substitute, expanding the structural diversity of biologically active compounds. Despite its potential, norcamphane has received little synthetic attention, with related six-membered ring systems dominating research. Jørgensen <em>et al.</em> developed asymmetric synthesis of norcamphane using a <em>Cinchona</em>-derived amine, but its single-enantiomer nature limited pharmaceutical applications, and fumarates enable only limited enantioselectivity. Here, we introduce a highly selective approach using aminomefloquine as an organocatalyst and thiofumarates as electrophiles. Both aminomefloquine enantiomers efficiently catalyze the reaction, yielding norcamphane thioesters as single regio- and diastereoisomers in both enantiomeric forms. This strategy overcomes previous limitations, offering improved selectivity and broader applicability. Moreover, thioesters act as versatile oxo-ester equivalents with enhanced reactivity. We also show that the yields can be improved by mechanochemical methods (ball milling) when compared to solution phase reactions, albeit with slightly lower enantioselectivity. Finally, based on dispersion-corrected density functional theory (DFT) calculations, we demonstrate that the mechanism can be classified as stepwise subsequent Michael additions, with the amine playing a dual role in enamine and imine formation, ensuring facial selectivity. The proposed computational protocol allowed us to accurately reproduce specific product yields based on kinetic modelling, and it can be further used to scan for other effective variants and catalysts for related reactions. This work presents catalysts that operate <em>via</em> the same molecular principles as 9-amino-9-deoxy-<em>epi</em>-quinine, enabling the efficient synthesis of bicyclic ring systems and expanding the scope of organocatalytic strategies.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":" 19","pages":" 5124-5135"},"PeriodicalIF":4.7,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qo/d5qo01014d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Substrate-Controlled Regioselective Dibenzylation of Enaminones","authors":"Xiuju Wang, Jin Zhang, Xingyu Zhao, Yiran Wang, Jinwen Sima, Zihan Wang, Xue Jia, Siyu Song, Fuchao Yu","doi":"10.1039/d5qo00972c","DOIUrl":"https://doi.org/10.1039/d5qo00972c","url":null,"abstract":"A substrate-controlled α,α-dibenzylation and O-benzylation-α-benzylation reaction of enaminones with benzyl bromides has been described. This divergent strategy provides efficient access to a new class of structurally diverse α,α-dibenzylated products and O-benzylated-α-benzylated products through adjusting the alkyl or aryl substituent at the β-position of enaminones. This protocol represents the first example of transition-metal-free-catalyzed and regioselective dibenzylation reactions of alkenes. This approach is notable for mild and operationally simple conditions, good functional group tolerance, gram-scale reaction and late-stage derivatization.2","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719486","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}

{"title":"Origin of ligand-controlled regioselectivity in Co-catalyzed borylation of fluorinated arenes","authors":"Xiaofang Zhai, Han Gao, Feng Ye, Wujie Wang, Yuliang Li, Gang Lu","doi":"10.1039/d5qo00897b","DOIUrl":"https://doi.org/10.1039/d5qo00897b","url":null,"abstract":"The mechanism and origins of regioselectivity in cobalt-catalyzed borylation of fluorinated arenes were computationally investigated. The results reveal that cobalt catalysts bearing two distinct pincer ligands exhibit different regioselectivity-determining steps. The ortho-selective borylation observed with the (PNP)Co catalyst is attributed to stronger electronic interactions in the σ-bond metathesis transition state. In contrast, the meta-selective borylation favored by the (CNC)Co catalyst arises from weaker electrostatic repulsion and enhanced charge transfer effects in the C–H oxidative addition transition state.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719492","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}

{"title":"Visible-light or sunlight-driven copper catalysis for base-free synthesis of β-diketones via radical acylation of enol silyl ethers","authors":"Xun Yang, Ming-Yang Yang, Siyi Qin, Haiyan Li, Wengui Duan, Jingshu Han, Lin Yu","doi":"10.1039/d5qo00827a","DOIUrl":"https://doi.org/10.1039/d5qo00827a","url":null,"abstract":"A mild and sustainable method for the synthesis of β-diketones has been developed via visible-light- or sun-light-driven, copper-catalyzed acylation of enol silanes with acyl chlorides. This protocol departs from traditional two-electron pathways by employing a radical-mediated role-reversal strategy that effectively suppresses side reactions such as over-acylation and oxo-acylation. The reaction proceeds under operationally simple conditions and allows for gram-scale synthesis. Furthermore, the resulting β-diketones, as versatile synthetic intermediates, were readily converted into α-diketones, enamine derivatives and heterocyclic scaffolds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"65 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144715652","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}

{"title":"NHC/Photoredox Dual Catalysis Directs N-methyl Radical Coupling for Decarboxylative Synthesis of α-N-Aryl amino Ketones","authors":"Wenying Zhao, Weikun Zeng, Shilin Zhou, Jun Zhou, Yi Jin","doi":"10.1039/d5qo00923e","DOIUrl":"https://doi.org/10.1039/d5qo00923e","url":null,"abstract":"Herein, a synergistic NHC/photoredox system enables α-arylamino ketone synthesis via stabilized N-methyl radical intermediates, overcoming competitive dimerization. Key innovations include base-mediated N-methyl radical generation and acyl azolium intermediate-guided cross-coupling, steering reactivity away from parasitic pathways. Electron-rich NHCs (e.g., Mes-substituted) accelerating acyl azolium intermediate formation, achieving broad substrate scope under mild conditions. Mechanistic studies confirm radical intermediates, while derivatization highlights utility in bioactive molecule synthesis. This strategy merges atom economy with scalable, step-economy catalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719488","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}

{"title":"Synthesis of Multisubstituted Cyclohexenes and Cyclopentenes via Cascade Michael/Aldol/Annulative SuFEx/β-Sultone Desulfonation of β-Arylethenesulfonyl Fluorides","authors":"Fang Zhang, Qichao Zhang, Pei Xie, Qifan Wang, Lin He, Zhihua Cai, Guangfen Du","doi":"10.1039/d5qo00837a","DOIUrl":"https://doi.org/10.1039/d5qo00837a","url":null,"abstract":"The first β-sultone desulfonation facilitated diastereoselective synthesis of functional cyclohexenes and cyclopentenes is described. Under the mediation of Cs2CO3, γ-ketomalononitriles reacted with β-arylethenesulfonyl fluorides through a cascade Michael addition/aldol reaction/annulative SuFEx click reaction/β-sultone desulfonation process to afford functionalized cyclohexenes in 40-99% yields and excellent cis-selectivity. In addition, β-ketomalononitriles undergo similar cascade reaction with β-arylethenesulfonyl fluorides to produce functional cyclopentenes in 57-99% yields with excellent trans-selectivity. A possible mechanism was proposed based on control experiments and DFT calculations.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"144 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701967","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}

{"title":"Access to Chiral α-Methyl-α-Aryl Carboxylic Acids via Phosphoric Acid-Catalyzed Kinetic Resolution of Biaryl Oxazepines","authors":"Guimei Dai, Yifei Ma, Weiwei Tan, Ting Tu, Bowen Zhu, Zhikang Wei, Liejin Zhou, Shi-Chao Ren, Xing Yang","doi":"10.1039/d5qo00953g","DOIUrl":"https://doi.org/10.1039/d5qo00953g","url":null,"abstract":"We disclose herein a chiral phosphoric acid-catalyzed kinetic resolution of racemic biaryl oxazepines with alcohols, giving a series of biaryl oxazepines and imidate products bearing a chiral center in good yields and enantioselectivities. The racemic biaryl oxazepine substrates could be readily synthesized from racemic carboxylic acids. Hydrolysis of the chiral imidate products afforded α-methyl-α-aryl carboxylic acids in high yields and enantioselectivities.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702070","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}