{"title":"Site-selective α-C(sp3)–H bond functionalization of amines/amides via 1,2-hydrogen atom transfer","authors":"Dong Zou , Jiaqi Yao","doi":"10.1039/d6qo00382f","DOIUrl":"10.1039/d6qo00382f","url":null,"abstract":"<div><div>Site-selective functionalization of C(sp<sup>3</sup>)–H bonds represents a core challenge in modern organic synthesis. The strategy of nitrogen-centered radical-mediated 1,2-hydrogen atom transfer (1,2-HAT) provides an efficient new pathway for the precise α-C(sp<sup>3</sup>)–H bond functionalization of amines/amides. This article systematically reviews the latest research advances in this field, with a focus on the design and development of nitrogen radical precursors such as <em>N</em>-aroyloxyamides, <em>N</em>-aryloxyamides, <em>N</em>-alkoxyamides, and hydroxamic esters. It delves into the reaction mechanisms and the principles governing chemoselectivity in 1,2-HAT processes under photoredox catalysis, transition-metal-free conditions, and transition-metal synergistic catalysis. The review summarizes the applications of this strategy in the construction of C–C bonds and carbon–heteroatom bonds, highlighting its core advantages, including mild reaction conditions, excellent functional group tolerance, high site selectivity, and applicability in the late-stage functionalization of complex molecules. Finally, the current challenges in this field are analyzed, and future research directions and application prospects are discussed.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3802-3824"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yongwei Qian , Shengyang Huang , Shengwen Li , Zhenzhuo Liu , Guangcheng Wu , Yingchun Liu , Jiyong Liu , Bin Sun , Ming Li , Hao Li
{"title":"A furan prism cage: synthesis, guest recognition, and applications in constructing charge-transfer co-crystals","authors":"Yongwei Qian , Shengyang Huang , Shengwen Li , Zhenzhuo Liu , Guangcheng Wu , Yingchun Liu , Jiyong Liu , Bin Sun , Ming Li , Hao Li","doi":"10.1039/d6qo00344c","DOIUrl":"10.1039/d6qo00344c","url":null,"abstract":"<div><div>Supramolecular hosts featuring well-defined cavities and electron-rich architectures are highly attractive for functional applications, yet their synthesis—particularly for three-dimensional organic cages—often relies on complex, irreversible reaction pathways. Herein, we report the synthesis of an electron-rich furan prism cage () bearing π-conjugated platforms and pillars, which displays strong host–guest affinities toward a broad range of guests, including both electron-deficient and electron-rich species. Single-crystal and solid–state studies reveal two distinct binding modes, corresponding to host–guest stoichiometries of 1 : 2 and 1 : 1. In the 1 : 2 complexes, one guest is encapsulated within the cavity while the second associates with the <em>exo</em>-wall of the cage, enabling the formation of ordered supramolecular networks through cooperative intra- and intermolecular π⋯π interactions. In contrast, the 1 : 1 binding mode leads to less ordered solid-state arrangements. Notably, complexation with electron-deficient guests, including 1,2,4,5-tetracyanobenzene () and tetrafluoroterephthalonitrile (), gives rise to pronounced charge-transfer interactions, which are manifested by distinct color changes, bathochromic shifts in solid-state absorption, and altered luminescence behaviors. One of these cage–guest complexes in the solid state demonstrates vapochromic behavior, whose color undergoes visible switching upon exposure to pyridine derivatives. These results demonstrate that precise control over host–guest stoichiometry and solid-state organization enables effective modulation of charge-transfer states, highlighting the potential of electron-rich three-dimensional cages as versatile platforms for charge-transfer-based optical materials.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3754-3762"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148261588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Recent developments in carbonyl–olefin metathesis","authors":"Lekkala Ravindar , Lekkala Revathi , Yee Ling Lau","doi":"10.1039/d5qo01435b","DOIUrl":"10.1039/d5qo01435b","url":null,"abstract":"<div><div>Due to its exceptional atom-economy and efficiency, the construction of C–C bonds <em>via</em> metathesis reactions between carbonyls and olefins has drawn significant attention in organic chemistry. Catalytic carbonyl–olefin metathesis processes are effective synthetic methods for the formation of alkenes. From stoichiometric reaction protocols to effective catalytic methods for ring-opening, ring-closing, and cross carbonyl–olefin metathesis, the field of carbonyl–olefin metathesis has experienced substantial growth in recent years. Hence, the current review aims to describe the development of strategies reported by researchers since 2020 for carbonyl–olefin metathesis reactions relying on ring-opening, ring-closing, and cross metathesis approaches. This review explores the scope and underlying mechanisms, providing a thorough understanding of the field's present strengths and limitations.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3846-3873"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yingyi Wang , Yaoyao Mei , Guilin Li , Feng Sha , Xinyan Wu
{"title":"Cascade reaction of 2-halo-4-alkenyloxazoles with arynes: a switchable divergent synthesis of 2-arylnaphtho[2,1-d]oxazoles, N-acylnaphthylamines, and α-halonaphthalenes","authors":"Yingyi Wang , Yaoyao Mei , Guilin Li , Feng Sha , Xinyan Wu","doi":"10.1039/d6qo00276e","DOIUrl":"10.1039/d6qo00276e","url":null,"abstract":"<div><div>A divergent synthesis of 2-arylnaphtho[2,1-<em>d</em>]oxazoles, <em>N</em>-acylnaphthylamines, and α-halonaphthalenes was achieved <em>via</em> a switchable transition-metal-free strategy based on the cascade reaction of arynes with 2-halo-4-alkenyloxazoles. Efforts have been made on the substrate design of 2-halo-4-alkenyloxazoles, in which the halogen atom on the 2-position serves as the versatile handle to unlock multiple reaction possibilities. Concurrently, precise control of the reaction pathway was achieved <em>via</em> the effective modulation of the reaction conditions. Notably, this strategy shows broad substrate compatibility, allowing the use of various 2-halooxazoles, including 2-chloro-, 2-bromo-, and 2-iodo-oxazoles. As a subsequent application development, a series of transformations were successfully realized on naphthoxazoles and polysubstituted naphthalenes, indicating the versatile application potential of the products. The initial bioactivity evaluation in cell-based assays demonstrated that 2-arylnaphtho[2,1-<em>d</em>]oxazoles and <em>N</em>-acylnaphthylamines have considerable antiproliferative activity against both human osteosarcoma cells and non-small cell lung carcinoma cells.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3609-3618"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147755315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Justin Kahle , Niklas J. Hermann , Martin C. Dietl , Patrick D. Römgens , Kim J. Warth , Christopher Hüßler , Alexandra V. Mackenroth , Fabian Baier , Ute Zschieschang , Petra Krämer , Frank Rominger , Matthias Rudolph , Hagen Klauk , Jana Zaumseil , A. Stephen K. Hashmi
{"title":"π-Extended dipyrrolopyrazines as multifunctional materials","authors":"Justin Kahle , Niklas J. Hermann , Martin C. Dietl , Patrick D. Römgens , Kim J. Warth , Christopher Hüßler , Alexandra V. Mackenroth , Fabian Baier , Ute Zschieschang , Petra Krämer , Frank Rominger , Matthias Rudolph , Hagen Klauk , Jana Zaumseil , A. Stephen K. Hashmi","doi":"10.1039/d6qo00350h","DOIUrl":"10.1039/d6qo00350h","url":null,"abstract":"<div><div>Here, we report a convergent synthetic strategy employing a gold-catalyzed cyclization to construct novel π-extended dipyrrolopyrazine () derivatives in a modular fashion. The robust design of <strong>s</strong> ensures high thermal stability, excellent oxidation resistance, and adaptability for integration into organic thin-film transistors and photoluminescent devices. Systematic exploration of substitution patterns revealed insights into structure–property relationships, particularly the influence of isosteric CH/N exchange. These findings establish <strong>s</strong> as a versatile platform for multifunctional materials, offering pathways for innovations in organic electronics.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3717-3727"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147751650","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hayoung Kim , Young-hwa Jin , Seonghun Kim , Jeong-Hun Sohn
{"title":"Transition-metal-free synthesis of bipyridines from pyridyl pyrimidylsulfones","authors":"Hayoung Kim , Young-hwa Jin , Seonghun Kim , Jeong-Hun Sohn","doi":"10.1039/d6qo00332j","DOIUrl":"10.1039/d6qo00332j","url":null,"abstract":"<div><div>We report a transition-metal-free cross-coupling of readily accessible pyridyl pyrimidylsulfones with azaaryl Grignard reagents that provides direct access to diverse bis-azaaryl products, including 2,2′-, 2,3′-, and 2,4′-bipyridines, under mild conditions, while also accommodating related azaaryl–heteroaryl products. The reaction proceeds through S<sub>N</sub>Ar activation of the pyrimidylsulfone to generate magnesium pyridyl sulfinates <em>in situ</em>, followed by desulfinative C–C bond formation. The synthetic utility of the method is demonstrated by regiodivergent access to bipyridines and the preparation of caerulomycin F.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 12","pages":"Pages 3774-3779"},"PeriodicalIF":0.0,"publicationDate":"2026-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148261589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Photoinduced sulfanyloximation of styrenes using N-nitrosamines and thiols","authors":"Ken Yamazaki , Toshiki Tamura , Shuta Akimoto , Tomoya Miura","doi":"10.1039/d6qo00315j","DOIUrl":"10.1039/d6qo00315j","url":null,"abstract":"<div><div>Molecules featuring both sulfur and nitrogen atoms are privileged scaffolds in medicinal chemistry and biological systems. However, methods for the direct and regioselective installation of these heteroatoms onto alkenes remain limited. Herein, we report a visible-light-induced, three-component sulfanyloximation of styrenes utilizing thiols and <em>N</em>-nitrosamine as a bench-stable nitrogen oxide (NO) surrogate. This regioselective protocol operates under mild conditions with remarkable functional group tolerance. The synthetic utility of this methodology is further demonstrated by its extension to the synthesis of 2,3-disubstituted indoles and the divergent downstream derivatization of α-sulfanyl ketoxime products <em>via</em> imidoyl fluoride intermediates. An extensive mechanistic investigation supports a pathway initiated by thiyl radical addition to alkenes followed by radical coupling with <em>in situ</em> generated NO.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 11","pages":"Pages 3367-3375"},"PeriodicalIF":0.0,"publicationDate":"2026-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147642051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Micelle-enabled Pd-catalyzed cross-coupling of arylthianthrenium salts in aqueous media","authors":"Vinothkumar Vinayagam , Subir Kumar Sadhukhan , Dhurwasulu Baledi , Shravan Kumar Avadhutha , Sai Kilari , Chittem Rajashekar Reddy , Vijayasaradhi Sivalenka","doi":"10.1039/d6qo00198j","DOIUrl":"10.1039/d6qo00198j","url":null,"abstract":"<div><div>A green approach for palladium-catalyzed cross-coupling of arylthianthrenium salts with aryl/heteroaryl boronic acids and terminal alkynes under micellar conditions has been developed. Biodegradable, abundant, and naturally available saponin is utilized as a surfactant that serves as a micellar-catalysis system, effectively promoting a C–C cross-coupling reaction in water at room temperature. The organic solvent-free saponin-mediated micellar-catalysis system promoted Suzuki–Miyaura and Sonogashira cross-coupling of an array of challenging heteroarene substrates. Other key features of this method include good functional group tolerance, amenability to scale-up, and recyclability of the reaction medium.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 11","pages":"Pages 3357-3366"},"PeriodicalIF":0.0,"publicationDate":"2026-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147642052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cristina Castanyer , Tània Pèlachs , Elias A. Romero-Cavagnaro , Clara Sabrià , Ferran Feixas , Xavi Ribas , Anna Roglans , Anna Pla-Quintana
{"title":"Supramolecular masks for the regioselective synthesis of Diels–Alder hetero-tris-adduct C60 fullerene","authors":"Cristina Castanyer , Tània Pèlachs , Elias A. Romero-Cavagnaro , Clara Sabrià , Ferran Feixas , Xavi Ribas , Anna Roglans , Anna Pla-Quintana","doi":"10.1039/d6qo00263c","DOIUrl":"10.1039/d6qo00263c","url":null,"abstract":"<div><div>Herein, we report the regioselective hetero-tris-functionalization of fullerenes <em>via</em> a sequential Diels–Alder cycloaddition strategy. The first addend is introduced onto C<sub>60</sub> through a cascade process involving a Ru-catalyzed cycloisomerization of 1,6-enynes, followed by a Diels–Alder reaction with C<sub>60</sub>. Subsequently, supramolecular nanocapsules are employed as regioselective masks, enabling enhanced control over the formation of a hetero-tris-adduct bearing two pentacene units. These units are positioned equatorially with respect to the initial addend and adopt a <em>trans</em>-1 relative orientation. Notably, a single pure tris-regioisomer, <em>e</em>,<em>e</em>,<em>t</em>1(<em>I</em>), is obtained for both and . Access to pure-isomer hetero-tris Diels–Alder adducts is unprecedented and highlights the broad potential of the supramolecular mask strategy.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 11","pages":"Pages 3341-3348"},"PeriodicalIF":0.0,"publicationDate":"2026-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147642053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Donghao Wang , Chenlu Zheng , Chao Shen , Min Wang , Jiabin Shen
{"title":"Metal-free, visible-light-driven multicomponent reactions of glycine derivatives with styrene and disulfide ether","authors":"Donghao Wang , Chenlu Zheng , Chao Shen , Min Wang , Jiabin Shen","doi":"10.1039/d6qo00317f","DOIUrl":"10.1039/d6qo00317f","url":null,"abstract":"<div><div>α-Amino acids and their derivatives are prevalent structural motifs with universal applications in drug discovery. Herein, we report metal free, visible-light-driven multicomponent reactions of glycine derivatives with styrene and disulfide ether. This protocol features mild and green conditions, appreciable functional group tolerance, and broad substrate scope, thus providing a sustainable and practical strategy to access synthetically valuable chalcogenated α-amino acid derivatives and peptide derivatives. Mechanistic investigations showed that an imine might be the key intermediate of this transformation.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 11","pages":"Pages 3468-3474"},"PeriodicalIF":0.0,"publicationDate":"2026-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147709111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}