Organic Chemistry Frontiers最新文献

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

Sulfonium salt formation-triggered regio-and Z-stereoselective phenoxythiolation of alkynes 磺盐形成引发的炔的区域和z型立体选择性苯氧噻唑化

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-22 DOI: 10.1039/d5qo00899a

Mengke Su, Hanmiao Xu, Zengwei Lai, Jian Wen

引用次数: 0

Correction: HBF4-mediated direct alcoholysis of amides under mild conditions 更正：在温和条件下hbf4介导酰胺直接醇解

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-22 DOI: 10.1039/d5qo90055g

Shi-Zheng Liu, Wen-Heng Liu, Yaotai Deng, Qiang Li, Ming-Yu Dou, Yu Cui, Jian-Min Dou

引用次数: 0

A main-chain [6]rotaxane: from synthesis to multi-stimuli-responsive motions 主链[6]轮烷：从合成到多刺激反应运动

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-22 DOI: 10.1039/d5qo00930h

Wentao Yu, Yidan Zhou, Zhiyao Yang, Juting Tan, Yimin Cai, Xiaowei Li, Wen Feng, Lihua Yuan

{"title":"A main-chain [6]rotaxane: from synthesis to multi-stimuli-responsive motions","authors":"Wentao Yu, Yidan Zhou, Zhiyao Yang, Juting Tan, Yimin Cai, Xiaowei Li, Wen Feng, Lihua Yuan","doi":"10.1039/d5qo00930h","DOIUrl":"https://doi.org/10.1039/d5qo00930h","url":null,"abstract":"The synthesis of higher order oligo[n]rotaxanes (usually n ≥ 3) featuring multi-stimuli responsive motions at the molecular level is critical for advancing artificial molecular machines and smart materials, yet achieving this goal remains a significant challenge. Herein, a main-chain [6]rotaxane and control [n]rotaxanes (n= 2, 3, and 4) were constructed with the assistance of templation by bipyridinium- or dialkylammonium-threaded two dimensional hydrogen-bonded (H-bonded) azo-macrocycles via Cu-mediated azide-alkyne cycloaddition reaction. The [6]rotaxane exhibits reversible multi-stimuli responsive motions triggered by acid-base reactions, solvent polarity changes, and light irradiation. Notably, three macrocycles (one ring A component and two ring B components), which are compactly stacked at the bipyridinium (BP2+) station owing to the large π-surface, act as a masked binding site to facilitate shuttling of the remaining two macrocycles (ring C components) driven by cooperative π-π stacking interactions. Morphological studies by SEM microscopy on the [6]rotaxane reveal that the supramolecular assemblies undergo reversible transitions between amorphous and spherical or nanorod nanostructures in solution. This work presents a rare example of using H-bonded aramide macrocycles for the construction of multi-stimuli responsive higher order rotaxanes, expanding the toolkits of supramolecular elements with controlled supramolecular structures.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678252","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

Computational investigation of palladium-catalyzed allene–allene cross-coupling 钯催化烯-烯交偶联的计算研究

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-22 DOI: 10.1039/d5qo00617a

Feiyun Jia, Chenghua Zhang, Yongsheng Yang, Xueting Zheng, shen mingjin, Jun Dong, Mingsong Shi

{"title":"Computational investigation of palladium-catalyzed allene–allene cross-coupling","authors":"Feiyun Jia, Chenghua Zhang, Yongsheng Yang, Xueting Zheng, shen mingjin, Jun Dong, Mingsong Shi","doi":"10.1039/d5qo00617a","DOIUrl":"https://doi.org/10.1039/d5qo00617a","url":null,"abstract":"The construction of [4]dendralenes poses a significant synthetic challenge. Palladium-catalyzed oxidative allene–allene cross-coupling offers high selectivity, but its mechanistic basis, competing pathways, and rate-determining step remain unclear. Herein, we investigate a palladium-catalyzed oxidative allene–allene cross-coupling mechanism using density functional theory (DFT) methods. Two competing pathways (Pathway1 and Pathway2) for R groups on the trisubstituted allene reactant, bearing either a -CH₂-EWG (electron-withdrawing group) or -CH₂-Aryl substituent, were systematically evaluated. Computational results show that Pathway2, involving selective allenic α-C-H bond cleavage in the β-H elimination step, is kinetically favored (ΔΔG‡ = 7.3 kcal mol⁻¹), strongly correlating with experimental observations. Carbopalladation (ΔG‡ = 22.8 kcal mol⁻¹) is identified as the rate-determining step (RDS) for both Pathway 1 and Pathway 2. Mechanistic analysis rationalizes the remarkable selectivities of this strategy, including (i) regioselective C–H activation, (ii) cross-selective carbocyclization–carbopalladation, and (iii) stereoselective cis/trans isomerism. The literature gap—specifically, the lack of mechanistic understanding of selectivity in palladium-catalyzed oxidative allene-allene cross-coupling, including unresolved questions about competing pathways and rate-determining steps—has been clearly explained. Furthermore, we reveal the pivotal role of the allylic directing group, which facilitates C–H activation through a synergistic Pd-π interaction. Distortion-interaction(D/I) analysis analysis revealed that higher distortion energy is responsible for this regioselectivity. This work provides atomic-level insights into the design of dendralene architectures and broadens the scope of stereocontrolled polyene synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"212 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678256","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

Rh2(II)-catalyzed cyclization/gem-hydrosilylation of benzene-fused 1,6-enynones Rh2（II）催化苯融合1,6-烯酮的环化/宝石硅氢化反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-07-22 DOI: 10.1039/d5qo00835b

Zurong Xu, Jiajun Lu, Rui Wu, Shifa Zhu

引用次数: 0