Hongyan Zhang, Ming Li, Li Shao, Haozhong Liang, Bin Hua, Niveen M. Khashab, Feihe Huang
{"title":"Selective separation of meta- and para-cresol using nonporous adaptive crystals of perpropoxylated pillar[5]arene","authors":"Hongyan Zhang, Ming Li, Li Shao, Haozhong Liang, Bin Hua, Niveen M. Khashab, Feihe Huang","doi":"10.1039/d5qo00620a","DOIUrl":"https://doi.org/10.1039/d5qo00620a","url":null,"abstract":"The selective separation of meta-cresol (MC) and para-cresol (PC) remains a significant challenge due to their nearly identical physicochemical properties. Here, we report nonporous adaptive crystals (NACs) based on perpropoxylated pillar[5]arene (PrP5) for the efficient and selective adsorption of MC over PC. Specifically, PrP5 crystals demonstrate exceptional selectivity, achieving 94.00% purity in the separation of MC from an equimolar MC/PC mixture while maintaining robust regenerability across multiple cycles. Furthermore, the incorporation of PrP5 into a molecular sieve facilitates the selective removal of trace MC impurities, enhancing PC purity from 98.40% to 99.06% in a single cycle. These findings underscore the potential of PrP5-based NACs as a promising material for the separation and high-purity purification of compounds in industrial processes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143979492","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}
Jia-Xuan Luo, Ze Zhuang, Yu-Zhang Huang, Xiaohui Kang, Yong Luo
{"title":"Pyrrolyl radical-involved di-/tri-functionalization of alkenes by sulfonyl pyrroles via radical/radical cross-coupling","authors":"Jia-Xuan Luo, Ze Zhuang, Yu-Zhang Huang, Xiaohui Kang, Yong Luo","doi":"10.1039/d5qo00557d","DOIUrl":"https://doi.org/10.1039/d5qo00557d","url":null,"abstract":"Installation of a pyrrolyl group on the adjacent position of an electron-withdrawing group presents significant challenges, as either the electrophilic or radical addition to pyrrole is suffered from some drawbacks. Herein, by using the sulfonyl pyrrole as the novel precursor of sulfonyl radical and pyrrolyl radical, a visible light-mediated radical/radical cross-coupling strategy has been developed to construct dipyrrolyl acetonitriles and benzhydryl pyrroles in good efficiency. This success highlighted the utilization of carbon-centered pyrrolyl radical derived from N–S bond activation in synthetic chemistry. This protocol broadened the transformations of sulfonamides and achieved multi-functionalization of alkenes to build quaternary carbon centers. DFT calculation demonstrated that the energy transfer between the excited photocatalyst and sulfonyl pyrrole contributed to N–S bond cleavage and resulted in pyrrolylation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"81 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143979494","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":"Modular Access to Functionalized Azetidines via Electrophilic Azetidinylation","authors":"Dayu Tian, Guang Chen, Xian Xiao, Xiaocheng Wang, Hai-Jun Zhang","doi":"10.1039/d5qo00552c","DOIUrl":"https://doi.org/10.1039/d5qo00552c","url":null,"abstract":"General methods for the rapid and direct incorporation of unconventional ring motifs into core scaffolds are highly sought-after in medicinal chemistry. However, approaches enabling the direct attachment of privileged azetidine rings to the oft-encountered biorelevant nucleophiles remain elusive. Here, we report an electrophilic azetidinylation strategy leveraging the underexplored reagents azetidinyl trichloroacetimidates and the novel reagents azetidinyl o-alkynylbenzoates, allowing for the “any-stage” installation of azetidine rings. A wide range of nucleophiles can be readily azetidinylated, providing a diverse library of functionalized 3-aryl and 3-alkyl azetidines. The power of this method is further demonstrated by the simplified synthesis of multiple medicinally relevant structures and the facile access to azetidine analogues for bioactive compounds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"55 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143979493","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":"Brønsted acid enabled metal-free remote oxygenation and amidation of unstrained C–C bonds via 1,4-group migration chaperoned radical-polar crossover","authors":"Xiaofei Xie, yun Shi, Yukun Li, Jinge Gui, Yingguang Zhu, Kang Chen","doi":"10.1039/d5qo00549c","DOIUrl":"https://doi.org/10.1039/d5qo00549c","url":null,"abstract":"C–C bond functionalization has emerged as a powerful tool for the skeleton editing of organic molecules. However, remote C(sp3)–O and C(sp3)–N bonds formation via unstrained C–C bond cleavage in acyclic molecules still remains challenging. Herein in this work, a Brønsted acid enabled metal-free remote oxygenation and amidation of NHPI esters via 1,4-group migration chaperoned radical-polar crossover has been established, affording a variety of heteroaryl-tethered alcohols, ethers and amides in moderate to good yields. This protocol also features mild conditions, good functional group tolerance and high regioselectivity, proving a novel paradigm for remote C(sp3)–heteroatom bond construction via C–C bond activation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945844","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}
Cui Zhang, Yun-Tao Shen, Ning-Xin Xia, Xin-Song Zhou, Li-Bo Yang, Jia Hu, Ya-Min Li
{"title":"Cascade cyclization/fluoromethylthiolation of alkynes, unsaturated α‑bromocarbonyls and PhSO2SRF","authors":"Cui Zhang, Yun-Tao Shen, Ning-Xin Xia, Xin-Song Zhou, Li-Bo Yang, Jia Hu, Ya-Min Li","doi":"10.1039/d5qo00585j","DOIUrl":"https://doi.org/10.1039/d5qo00585j","url":null,"abstract":"A copper-catalyzed cyclization/fluoromethylthiolation cascade of alkynes, unsaturated α‑bromocarbonyls and PhSO2SCF2H/PhSO2SCF3 has been developed for access to fluoromethylthiolated cyclopentenes and cyclohexenes. The present reaction enables the construction of three new chemical bonds in a single step through the addition of alkyl radicals across alkynes, followed by cyclization and fluoromethylthiolation. It is characterized by high chemoselectivity and a broad substrate scope.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"58 2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945585","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":"Active Electropositive α-Chlorine: Trichloroacetonitrile as an Electrophilic Chlorination Reagent","authors":"Bingxing Zhou, Lei Bai, Changming Xu","doi":"10.1039/d5qo00379b","DOIUrl":"https://doi.org/10.1039/d5qo00379b","url":null,"abstract":"An inverse-electron C-Cl bond cleavage of Cl3CCN under basic conditions to give chlorine cation was disclosed. The generated chlorine cation can be used for electrophilic α-mono- and α-dichlorination of various carbonyl compounds in the presence of catalytic or stoichiometric amount of base, which represents one of the few electrophilic chlorination methods using cheap, commercially available and atom-economical C-chloro reagent.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945611","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}
Ji Yang, Zhenni He, Zhen Yao, Wei Huang, Siwen Meng, Lijin Xu, Qing-Hua Fan
{"title":"Rhodium-catalyzed one-pot tandem reductive amination/asymmetric transfer hydrogenation of quinoxaline-2-carbaldehydes and anilines for the efficient synthesis of chiral vicinal diamines","authors":"Ji Yang, Zhenni He, Zhen Yao, Wei Huang, Siwen Meng, Lijin Xu, Qing-Hua Fan","doi":"10.1039/d5qo00625b","DOIUrl":"https://doi.org/10.1039/d5qo00625b","url":null,"abstract":"Enantioselective synthesis of chiral <em>N</em>,<em>N</em>′-diaryl vicinal diamines <em>via</em> Cp*Rh-catalyzed one-pot tandem reductive amination/asymmetric transfer hydrogenation of quinoxaline-2-carbaldehydes with anilines using HCO<small><sub>2</sub></small>H/NEt<small><sub>3</sub></small> (5/2) as the reductant has been developed. This mild catalytic system exhibits broad substrate generality and efficiently produces diversely substituted chiral <em>N</em>,<em>N</em>′-diaryl vicinal diamines with opposite configurations in high yields and excellent enantioselectivities (up to >99% ee). The synthetic utility of this protocol has been validated through successful gram-scale synthesis and facile derivatization of the resulting chiral vicinal diamines.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940547","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":"Reagent-controlled Selective Synthesis of Sulfinamides and Sulfoximines from tert-Butanesulfinamide","authors":"Wenbo Zhang, Yanhua Ouyang, Xi Zou, Bing Gao","doi":"10.1039/d5qo00573f","DOIUrl":"https://doi.org/10.1039/d5qo00573f","url":null,"abstract":"The preparation of optically pure sulfinamides from <em>tert</em>-butanesulfinamide previously involved multi-step sequences, including the incorporation of desired chemical fragments to and subsequent removal of <em>tert</em>-butyl group from the sulfur center. We disclose a step-economic method herein that can accomplish these transformations in a single reaction. The formal <em><small><sup>t</sup></small></em>Bu-to-Ar exchange reaction of <em>tert</em>-butanesulfinamide is achieved using aryldiazonium reagents and copper catalyst. The catalyst and additives are crucial for the success of this method. Alternatively, slight modification to reaction conditions results in the formation of <em>tert</em>-butanesulfoximines, which are likely the transient precursors of <em><small><sup>t</sup></small></em>Bu-to-Ar exchange to give sulfinamides via <em>in situ</em> debutylation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940555","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}
Sophia Thiele, Michael Giffin, Matthieu Wendling, Daniel Görl, Christopher Plummer, Holger Frauenrath
{"title":"Polymer-Bridged Nanofibrils in a High-Molar-Mass Polyester via Co-assembly of Benzenetricarboxamide End Groups and Additive","authors":"Sophia Thiele, Michael Giffin, Matthieu Wendling, Daniel Görl, Christopher Plummer, Holger Frauenrath","doi":"10.1039/d5qo00087d","DOIUrl":"https://doi.org/10.1039/d5qo00087d","url":null,"abstract":"Benzenetricarboxamide (BTA) derivatives are versatile compounds widely employed as nucleating agents in commercial semicrystalline plastics and as supramolecular ligands in self-assembling telechelic polymer-based organogels, hydrogels, and bulk elastomers. However, their effectiveness as supramolecular modifiers is typically limited to low-molar-mass apolar polymers. Here, we report the supramolecular aggregation of a BTA-end-functionalized semicrystalline aliphatic polyester with a number-average molar mass several times its entanglement molar mass, blended with a matching low-molar-mass BTA additive. In these blends, the BTA end groups and additive co-assemble to form a new phase comprising a network of polymer-bridged nanofibrils. This network gives rise to a high-melt-strength rubbery regime that is absent from the pure telechelic polyester but extends to temperatures well above its melting point in the blends. Moreover, the nanofibrils prove to be highly efficient nucleating agents for crystallization of the polyester, significantly outperforming bulk additive precipitates. Our findings hence demonstrate that co-assembly of polymer end groups with a low-molar-mass additive may facilitate supramolecular aggregate formation in polymer matrices where endmodification alone is insufficient, leading to materials with increased melt strength, crystallization rates, and thermal dimensional stability, and hence valuable benefits for industrial applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940607","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":"Organo-mediator enabled electrochemical 1,4-aryl migration of N-aryl-2-iodobenzamides/N-sulfonyl-2-iodoanilines to access biaryls","authors":"Xiao-Qing Xie, Li-Tong Xiao, Wei Zhou, Yanli Wu, Haixin Ding, Ruchun Yang, Xian-Rong Song, Mu-Jia Luo, Qiang Xiao","doi":"10.1039/d5qo00484e","DOIUrl":"https://doi.org/10.1039/d5qo00484e","url":null,"abstract":"Herein, an electroreductive radical 1,4-aryl migration of N-aryl-2-iodobenzamides/N-sulfonyl-2-iodoanilines promoted by catalytic amounts of 9-bromophenanthrene as redox mediator is described. This protocol proceeds smoothly in an undivided cell under mild conditions, producing a wide range of structurally versatile biaryls in moderate to good yields without any transition metal catalysts, chemical reductants, or sacrificial anodes. Preliminary mechanistic studies revealed that the generation of aryl radical via cathodic single-electron reduction is crucial, with sequential intramolecular 5-exo-trig spirocyclization, C-N bond cleavage, and hydrogen atom abstraction.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"54 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940572","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}