Organic Chemistry Frontiers最新文献_第2页

Tunable thiofumarate stereoselective cycloadditions via aminomefloquine catalysis 氨基氟喹催化的可调异马酸硫代酯立体选择性环加成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-29 DOI: 10.1039/d5qo01014d

Radosław Suchanek, Michał Błauciak, Anna Spyszkiewicz, Błażej Dziuk, Przemysław J. Boratyński, Rafał Szabla, Rafał Kowalczyk

{"title":"Tunable thiofumarate stereoselective cycloadditions via aminomefloquine catalysis","authors":"Radosław Suchanek, Michał Błauciak, Anna Spyszkiewicz, Błażej Dziuk, Przemysław J. Boratyński, Rafał Szabla, Rafał Kowalczyk","doi":"10.1039/d5qo01014d","DOIUrl":"https://doi.org/10.1039/d5qo01014d","url":null,"abstract":"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 et al. developed asymmetric synthesis of norcamphane using a Cinchona-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 via the same molecular principles as 9-amino-9-deoxy-epi-quinine, enabling the efficient synthesis of bicyclic ring systems and expanding the scope of organocatalytic strategies.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Substrate-Controlled Regioselective Dibenzylation of Enaminones 底物控制的胺酮的区域选择性二苄基化

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-29 DOI: 10.1039/d5qo00972c

Xiuju Wang, Jin Zhang, Xingyu Zhao, Yiran Wang, Jinwen Sima, Zihan Wang, Xue Jia, Siyu Song, Fuchao Yu

引用次数: 0

Origin of ligand-controlled regioselectivity in Co-catalyzed borylation of fluorinated arenes 氟化芳烃共催化硼化反应中配体控制区域选择性的来源

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-28 DOI: 10.1039/d5qo00897b

Xiaofang Zhai, Han Gao, Feng Ye, Wujie Wang, Yuliang Li, Gang Lu

引用次数: 0

Visible-light or sunlight-driven copper catalysis for base-free synthesis of β-diketones via radical acylation of enol silyl ethers 烯醇硅基醚自由基酰化反应无碱合成β-二酮的可见光或日光驱动铜催化

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-28 DOI: 10.1039/d5qo00827a

Xun Yang, Ming-Yang Yang, Siyi Qin, Haiyan Li, Wengui Duan, Jingshu Han, Lin Yu

引用次数: 0

NHC/Photoredox Dual Catalysis Directs N-methyl Radical Coupling for Decarboxylative Synthesis of α-N-Aryl amino Ketones NHC/光氧化还原双催化引导n -甲基自由基偶联脱羧合成α- n -芳基氨基酮

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-28 DOI: 10.1039/d5qo00923e

Wenying Zhao, Weikun Zeng, Shilin Zhou, Jun Zhou, Yi Jin

引用次数: 0

Synthesis of Multisubstituted Cyclohexenes and Cyclopentenes via Cascade Michael/Aldol/Annulative SuFEx/β-Sultone Desulfonation of β-Arylethenesulfonyl Fluorides β-芳基磺酰氟级联Michael/Aldol/环结SuFEx/β-磺酮脱硫合成多取代环己烯和环戊烯

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-25 DOI: 10.1039/d5qo00837a

Fang Zhang, Qichao Zhang, Pei Xie, Qifan Wang, Lin He, Zhihua Cai, Guangfen Du

引用次数: 0

Access to Chiral α-Methyl-α-Aryl Carboxylic Acids via Phosphoric Acid-Catalyzed Kinetic Resolution of Biaryl Oxazepines 手性α-甲基-α-芳基羧酸的磷酸催化动力学拆分

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-25 DOI: 10.1039/d5qo00953g

Guimei Dai, Yifei Ma, Weiwei Tan, Ting Tu, Bowen Zhu, Zhikang Wei, Liejin Zhou, Shi-Chao Ren, Xing Yang

引用次数: 0

Utilisation of CO2 in the Simultaneous Installation of the C—C and C=C Bonds of α,β-Unsaturated Carboxylic Acids 利用CO2同时安装α，β-不饱和羧酸的C - C和C=C键

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-23 DOI: 10.1039/d5qo00770d

Amy Lowry, rachel E Lynch, Gerard P. McGlacken, Peter Byrne

{"title":"Utilisation of CO2 in the Simultaneous Installation of the C—C and C=C Bonds of α,β-Unsaturated Carboxylic Acids","authors":"Amy Lowry, rachel E Lynch, Gerard P. McGlacken, Peter Byrne","doi":"10.1039/d5qo00770d","DOIUrl":"https://doi.org/10.1039/d5qo00770d","url":null,"abstract":"Development of methods for the conversion of CO2 (a major waste product) into value-added chemicals has become an area of great interest. Herein we report the development of a new retrosynthetic double disconnection strategy, translating to a highly efficient synthetic methodology in which both the C=C double bond and the C—C bond of an α,β‑unsaturated carboxylic acid can be constructed concurrently, with CO2 as a chemical feedstock. Central to the success of this methodology are “phosphonium carboxylate ylides”. These unique new entities can undergo novel Wittig-type reactions, forming α,β‑unsaturated carboxylic acids with excellent stereoselectivity and perfectly regioselective installation of both the carboxyl group and the C=C bond. The α,β‑unsaturated carboxylic acid motif appears widely in the structures of pharmaceutical compounds and precursors thereof. The availability of a broadly applicable approach for synthesising α,β‑unsaturated carboxylic acids will thus be highly valuable. Surprisingly, this represents the first general direct Wittig-type methodology for formation of the alkene moiety in α,β‑unsaturated carboxylic acids.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694166","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

Intramolecular Exciplex Formation Between Pyrene and Tetraazapyrene in Supramolecular Assemblies 超分子组装中芘和四氮芘分子内杂络合物的形成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-23 DOI: 10.1039/d5qo00941c

Xinyi Liu, Camila Negrete-Vergara, Simon Matthias Langenegger, Lorraine A. Malaspina, Simon Grabowsky, Robert Häner, Shi-Xia Liu

{"title":"Intramolecular Exciplex Formation Between Pyrene and Tetraazapyrene in Supramolecular Assemblies","authors":"Xinyi Liu, Camila Negrete-Vergara, Simon Matthias Langenegger, Lorraine A. Malaspina, Simon Grabowsky, Robert Häner, Shi-Xia Liu","doi":"10.1039/d5qo00941c","DOIUrl":"https://doi.org/10.1039/d5qo00941c","url":null,"abstract":"Tetraazapyrene (TAP), a nitrogen-substituted analogue of pyrene, features a planar and electron-deficient π-conjugation system, and thus can act as a π-electron-acceptor. Despite its unique electronic properties, it remains underexplored due to synthetic challenges and limited derivatization methodologies. Herein, we report the first report of the selective cascade bromination of the TAP core in the presence of dibromoisocyanuric acid, affording 4,9-dibromo-TAP as a key intermediate. This precursor was subsequently employed to construct a novel pyrene-TAP-pyrene trimer (1), in which a central TAP core is flanked by two pyrene units via phosphodiester linkages. Similar to its all-pyrene-based analog in aqueous medium, this trimer undergoes temperature-triggered self-assembly via inter- and intramolecular non-covalent interactions, leading to the formation of supramolecular polymers featured with a donor-acceptor-donor architecture. Upon self-assembly, trimer 1 exhibits distinct optical responses, including enhanced monomeric pyrene fluorescence and unique exciplex emission. These phenomena are attributed to enhanced electronic interactions between pyrene and TAP cores facilitated by their close spatial arrangement in the resulting nanostructures. Our findings demonstrate the reversible and tunable nature of self-assembled nanostructures, highlighting their potential in the development of stimuli-responsive materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"278 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694168","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

Electrostatic interaction-assisted regiospecific and oxidant free [4+2] annulation enabled by RhIII catalyzed C−H bond activation 静电相互作用辅助的区域特异性和无氧化剂的[4+2]环化由RhIII催化的C−H键激活实现

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-23 DOI: 10.1039/d5qo00765h

Xiaogang Cui, Renyi Diao, Rui Ma, Minglong Zhang, Chuan Zhu, Cheng-Qiang Wang, Chao Feng

引用次数: 0