Fang Zhang, Qichao Zhang, Pei Xie, Qifan Wang, Lin He, Zhihua Cai, Guangfen Du
{"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}
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}
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}
{"title":"Electrostatic interaction-assisted regiospecific and oxidant free [4+2] annulation enabled by RhIII catalyzed C−H bond activation","authors":"Xiaogang Cui, Renyi Diao, Rui Ma, Minglong Zhang, Chuan Zhu, Cheng-Qiang Wang, Chao Feng","doi":"10.1039/d5qo00765h","DOIUrl":"https://doi.org/10.1039/d5qo00765h","url":null,"abstract":"A RhIII-catalyzed intermolecular [4+2] annulation reaction, employing N-tosylamide and carboxyl as the directing groups, has been developed herein. The utilization of readily accessible propargylic aminium triflate salts as coupling partners enables a highly efficient strategy for the regiospecific synthesis of isoquinolones and isocoumarins under oxidant-free conditions. In addition, this method is characterized by its facile substrates availability and broad functionality tolerance. Furthermore, preliminary control experiments reveal that electrostatic interaction plays a pivotal role in achieving the reversed regioselectivity observed in this transformation, setting it apart from previous related studies.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684918","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":"Sulfonium salt formation-triggered regio-and Z-stereoselective phenoxythiolation of alkynes","authors":"Mengke Su, Hanmiao Xu, Zengwei Lai, Jian Wen","doi":"10.1039/d5qo00899a","DOIUrl":"https://doi.org/10.1039/d5qo00899a","url":null,"abstract":"Sulfonium salts formation-triggered regio-and Z-stereoselective phenoxythiolation of terminal alkynes with phenols and sulfoxides which allows the synthesis of sulfur-containing aryl alkenylethers under the mild one-pot reaction conditions is reported. This reaction is mild, highly practical, easy to manipulate and demonstrates a wide substrate range with good functional group tolerance, furnishing high regio- and Z-selective products in moderate to high yields. The synthetic utility of this approach is documented through gram-scale preparation, product derivatizations and late-stage modification of complex bioactive molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678253","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":"Correction: HBF4-mediated direct alcoholysis of amides under mild conditions","authors":"Shi-Zheng Liu, Wen-Heng Liu, Yaotai Deng, Qiang Li, Ming-Yu Dou, Yu Cui, Jian-Min Dou","doi":"10.1039/d5qo90055g","DOIUrl":"https://doi.org/10.1039/d5qo90055g","url":null,"abstract":"Correction for ‘HBF<small><sub>4</sub></small>-mediated direct alcoholysis of amides under mild conditions’ by Shi-Zheng Liu <em>et al.</em>, <em>Org. Chem. Front.</em>, 2025, https://doi.org/10.1039/d5qo00603a.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"45 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678251","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":"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 <strong>A</strong> component and two ring <strong>B</strong> components), which are compactly stacked at the bipyridinium (<strong>BP</strong><small><sup>2+</sup></small>) station owing to the large π-surface, act as a masked binding site to facilitate shuttling of the remaining two macrocycles (ring <strong>C</strong> 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}
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}
{"title":"Rh2(II)-catalyzed cyclization/gem-hydrosilylation of benzene-fused 1,6-enynones","authors":"Zurong Xu, Jiajun Lu, Rui Wu, Shifa Zhu","doi":"10.1039/d5qo00835b","DOIUrl":"https://doi.org/10.1039/d5qo00835b","url":null,"abstract":"Cyclization/hydrosilylation of 1,6-enynes represents a highly efficient and atom-economical strategy for constructing silyl-functionalized five-membered carbocyclic or heterocyclic structural units from simple acyclic subunits containing ene and yne fragments. In contrast to hydrosilylation at distinct unsaturated bonds of the enyne substrate, the addition of hydrogen and silicon to the same position (geminal addition) during cyclization remains underexplored. Herein, we report a dirhodium(<small>II</small>)-catalyzed cyclization/geminal hydrosilylation of 1,6-enynes that accommodates primary, secondary and tertiary silanes. This protocol not only enables the facile one-step synthesis of bicyclo[3.1.0]hexanone silanes but also provides access to novel naphthol-derived silanes. Notably, this work achieves an asymmetric variant of cyclization/geminal hydrosilylation for 1,6-enynes, expanding the synthetic utility of this transformation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678250","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}