{"title":"Modular synthesis of 2-arylpyridines metal free-four component [2 + 2 + 1 + 1] annulation","authors":"Yanfeng Ma,Rong Huang,Fuhong Xiao,Guo-Jun Deng","doi":"10.1039/d6qo00829a","DOIUrl":"https://doi.org/10.1039/d6qo00829a","url":null,"abstract":"We have developed a multi-component strategy for the synthesis of 2-arylpyridines via a formal [2 + 2 + 1 + 1] cyclization under metal-free conditions. This method employs readily available starting materials and proceeds under straightforward reaction conditions. The transformation exhibits excellent regioselectivity, affording a diverse array of 2-arylpyridine derivatives in good yields with broad functional group tolerance. This metal-free and operationally simple platform opens a new avenue for the synthesis of pyridine-containing functional molecules in materials science.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973542","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":"Skeletal editing of anthranils O-to-CN transmutation: access to ring-expanded quinazolines","authors":"Yongzhen Li,Zicheng Liao,Lijuan Zhou,Jiajin Luo,Saihui Song,Shuo-Wen Wang,Shi Tang","doi":"10.1039/d6qo00702c","DOIUrl":"https://doi.org/10.1039/d6qo00702c","url":null,"abstract":"Skeletal editing is a uniquely powerful tool in organic chemistry that simplifies the synthesis of complex molecules. Herein, we report a simple skeletal editing strategy of anthranils for the synthesis of quinazolines via O-to-CN transmutation, which utilizes diverse aldehydes (including alkyl, aryl, and heterocyclic) and amines (such as ammonium acetate and benzylamines) as carbon and nitrogen precursors. This method enables the synthesis of ring-expanded quinazolines through three distinct approaches under metal-free (even additive-free) conditions, and exhibits good chemoselectivity and broad functional group tolerance. Moreover, late-stage skeletal modification, preparation of pharmaceutical analogs, scaled-up synthesis, and derivatization of products further demonstrate the practicability of this strategy. Preliminary mechanistic studies reveal an atom replacement reaction involving a 6π-electrocyclization/dehydroaromatization or [4 + 2] cycloaddition/intramolecular ring-opening process.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"555 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973552","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}
Shuaichen Zhang,Mengdie Zhang,Jing Zhang,Cheng Wang,Yujie Li,Shang Gao,Aijun Lin,Peng Sun
{"title":"Sustainable metal- and base-free acylative Suzuki-type cross-coupling of carboxylic acids and boronic acids","authors":"Shuaichen Zhang,Mengdie Zhang,Jing Zhang,Cheng Wang,Yujie Li,Shang Gao,Aijun Lin,Peng Sun","doi":"10.1039/d6qo00799f","DOIUrl":"https://doi.org/10.1039/d6qo00799f","url":null,"abstract":"The development of efficient and sustainable strategies for ketone synthesis from ubiquitous carboxylic acids remains a desirable yet challenging goal. While transition metal-catalyzed acylative Suzuki couplings offer a powerful means to construct C(acyl)–C bonds, issues such as residual metal contamination in products and waste generation limit their appeal. Herein, we report an efficient, metal-free protocol for the direct synthesis of ketones from carboxylic acids and (hetero)arylboronic acids, mediated by Tf2O and proceeding via a 1,3-boronate shift of tetracoordinate boron species. Direct coupling of carboxylic acids with boronic acids provides an innovative paradigm for ketone synthesis, offering enhanced substrate scope, exceptional step/atom economy, and simplified operational protocols. The utility of this platform is further demonstrated through the streamlined synthesis of pharmaceutically relevant compounds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"470 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973554","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}
Iván Cheng-Sánchez,Irama Fuentes-Pino,Mohamed El Hllafi,Federico Moya-Utrera,J. Manuel López-Romero,Amelia Díaz-Morilla,Antonio Sánchez-Ruiz,Michio Kurosu,Francisco Sarabia
{"title":"From nature to synthetic analogues: recent advances in the design and synthesis of natural product-based libraries","authors":"Iván Cheng-Sánchez,Irama Fuentes-Pino,Mohamed El Hllafi,Federico Moya-Utrera,J. Manuel López-Romero,Amelia Díaz-Morilla,Antonio Sánchez-Ruiz,Michio Kurosu,Francisco Sarabia","doi":"10.1039/d6qo00727a","DOIUrl":"https://doi.org/10.1039/d6qo00727a","url":null,"abstract":"The widely demonstrated value of natural products as valid starting points in the search for and identification of new drugs has driven the development of extensive libraries based on these natural products characterized by high structural diversity. Such libraries have played a pivotal role in elucidating robust structure–activity relationships (SARs), providing a critical foundation for subsequent drug development efforts. Various strategies have been delineated to streamline access to these libraries. This review reports recent advances and achievements in this area, which enhance the enduring significance of natural products in the discovery and development of new therapeutic agents.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"50 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973534","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}
Sergey P. Ivonin,Volodymyr V. Voloshchuk,Diana S. Stepanova,Svetlana V. Shishkina,Serhiy V. Ryabukhin,Dmytro M. Volochnyuk
{"title":"Synthesis of 3-formyl-6-azaindoles Vilsmeier–Haack formylation of 3-amino-4-methyl pyridines","authors":"Sergey P. Ivonin,Volodymyr V. Voloshchuk,Diana S. Stepanova,Svetlana V. Shishkina,Serhiy V. Ryabukhin,Dmytro M. Volochnyuk","doi":"10.1039/d6qo00452k","DOIUrl":"https://doi.org/10.1039/d6qo00452k","url":null,"abstract":"An efficient method for the preparation of 6-azaindoles bearing diverse 3-positional functionalities from commercially available reagents is described. The key transformation features a broad substrate scope and a simple experimental procedure, and can be easily scaled up to 100 g of the target formyl derivative. The structural characteristics of pyridine substrates that enable their successful use in the reaction were investigated and discussed. The collected observations were mechanistically rationalized, and the proposed mechanism was additionally confirmed by spectroscopic studies. UMAP chemoinformatic analysis demonstrated the broad utility of 3-functionalized-6-azaindoles as building blocks for expanding the MedChem-relevant chemical space using the REAL Database engine.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"140 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973536","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":"Ambient and aerobic C–N bond cleavage toward α-ketoester synthesis through LMCT excitation of CeCl","authors":"Jiabin Shen,Yezhe Zhao,Xiangbo Ma,Liangfeng Yang,Hao Xu,Chao Shen","doi":"10.1039/d6qo00851h","DOIUrl":"https://doi.org/10.1039/d6qo00851h","url":null,"abstract":"A sustainable method for converting acetophenones into α-ketoesters is reported through Ce(iii)-catalyzed oxidative C–N single-bond cleavage and esterification. Under mild conditions, this method achieves the selective cleavage of C–N bonds and the effective coupling of C–O bonds, demonstrating appreciable functional group tolerance, broad substrate scope, and significant potential for the late-stage modification of valuable natural products.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973541","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}
Suyu Ji,Zhiguo Zhang,Zhibin Sun,Kui Xue,Rupu Zhao,Xinrui Wang,Guisheng Zhang,Guangyue Bai
{"title":"Nucleophile-controlled divergent synthesis: photocatalyzed carboamination of allenes","authors":"Suyu Ji,Zhiguo Zhang,Zhibin Sun,Kui Xue,Rupu Zhao,Xinrui Wang,Guisheng Zhang,Guangyue Bai","doi":"10.1039/d6qo00656f","DOIUrl":"https://doi.org/10.1039/d6qo00656f","url":null,"abstract":"Controllable synthesis strategies provide an efficient and straightforward approach for the rapid construction of structurally diverse functional organic molecular frameworks from a single class of starting materials. The photo-induced radical addition of difluorobromides to allenes represents such a promising strategy. Herein, we demonstrate that following the radical addition of bromodifluoroacetamides to allenes, the newly formed radical intermediates can be oxidized to carbocations, which are subsequently attacked by amine nucleophiles to afford cyclic γ-lactams or linear amides bearing both fluorine and alkenyl moieties. Facilitated by visible light and iodide ions, this radical addition reaction occurs regiospecifically at the 1 and 2 positions of the allene compounds, and no addition products at other positions or nucleophilic adducts with mixed amine regioisomers are observed. This reaction features broad substrate scope, exceptional functional group tolerance, and facile post-functionalization, delivering fluorine-containing products with important biological and functional properties. Thus, this methodology exhibits promising application potential in materials science, agrochemistry, and medicinal chemistry.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"54 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973543","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":"Biomimetic asymmetric total syntheses of myrtucommulone J and myrtucyclitones A–D with anti-leukemic activity","authors":"Yan-Yi Wu,Shi-Lin Lin,Shanshan Song,Chao Yang,Xulin Han,Mei-Qi Zheng,Yanli Jin,Wen-Jing Wang,Chuang-Chuang Li,Chang Liu,Lei Wang,Wen-Cai Ye,Min-Jing Cheng","doi":"10.1039/d6qo00786d","DOIUrl":"https://doi.org/10.1039/d6qo00786d","url":null,"abstract":"Bridged natural products present a formidable challenge to synthesis due to their inherent ring strain and multiple stereocenters. Herein, we present the first concise, asymmetric syntheses of the bridged polycyclic natural products myrtucyclitones A–B and D, as well as asymmetric syntheses of myrtucyclitone C and myrtucommulone J using a biomimetic synthetic strategy based on biogenetic building blocks. These syntheses were achieved in only four to six linear steps without protecting groups, enabled by a key [3 + 3] cyclization that rapidly assembles the bridged polycyclic architectures with a high overall yield and good diastereoselectivity. This crucial transformation was rationalized through quantum mechanical calculations. Notably, the five synthesized bridged natural products exhibited potent anti-leukemic activity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"88 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973561","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}
Sonam Chorol,Sharvan Kumar,Ch Mudasar Hussain,M. S. Krishna Kumar,Suvendu Dey,Pritam Mukhopadhyay
{"title":"The synthesis and isolation of three states of naphthalene dianhydride: radical ion, red-emissive and electron-rich zwitterion, and highly electron-deficient switchable states","authors":"Sonam Chorol,Sharvan Kumar,Ch Mudasar Hussain,M. S. Krishna Kumar,Suvendu Dey,Pritam Mukhopadhyay","doi":"10.1039/d6qo00457a","DOIUrl":"https://doi.org/10.1039/d6qo00457a","url":null,"abstract":"Radical ions with reactive functional groups are challenging to isolate, but isolation along with their redox congeners can lead to the origination of intriguing opto-electronic features, novel supramolecular facets, and the realization of uncharted redox potentials. π-Conjugated anhydrides are yet to be stabilized and isolated in pure radical form, and their other redox states are yet to be isolated and investigated. Herein, we report the ambient isolation of a dianhydride radical ion (1˙+), its 2e−-reduced and electron-rich zwitterionic form (12±), and an extremely electron-deficient dication (12+) in three distinctly colored crystalline states. Notably, compared to reported diimide-based systems, the dianhydride radical ion exhibits red-shifted bands extending to the NIR region. Likewise, the doubly reduced dianhydride zwitterionic state also shows red-shifted absorption bands compared to direduced NDIs. The zwitterionic state also shows red emission extending to the NIR region. The zwitterionic state manifests a high HOMO energy level corresponding to −4.64 eV, which is comparable to the seminal e−-donor tetrathiafulvalene (TTF). The highly electron-deficient dicationic dianhydride exhibits exceptionally strong electron deficiency, superior to reported diimides, with a remarkably low electrochemically estimated LUMO energy of ∼−5.07 eV. Finally, we realized 2e− redox-driven aromaticity switching in the naphthalene rings of the zwitterion ↔ dication states. Such bottleable, crystalline multi-states with reactive functional groups can enable the expansion of the existing library of switchable open-/closed-shell states.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"144 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973564","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":"Pyrene-based photoresponsive materials: beyond luminescence","authors":"Junying Zhang,Xing-Dong Xu","doi":"10.1039/d6qo00640j","DOIUrl":"https://doi.org/10.1039/d6qo00640j","url":null,"abstract":"As an important class of stimuli-responsive luminescent materials, photoresponsive pyrene-based fluorescent materials exhibit broad application prospects in fields such as intelligent sensing, information encryption, biomedicine, and flexible electronics due to their unique photophysical properties, tunable aggregation behavior, and high sensitivity to external light stimuli. This article systematically reviews the research progress of photoresponsive pyrene-based fluorescent materials in recent years, focusing on four types of photoresponsive mechanisms: photodecomposition, photopolymerization, photoisomerization, and other composite response systems. It elaborates on the design strategies, photoresponsive behaviors, and applications of various materials in controlled drug release, information storage, circularly polarized luminescence, cell imaging, and self-healing materials. The article further summarizes the current challenges faced in this field, including molecular structure–activity relationships, response speed, cycling stability, and large-scale preparation. It also outlines future directions for development, such as guiding molecular design through theoretical calculations, developing near-infrared response systems, and expanding biomedical and information security applications. The aim is to provide references for the rational design and application innovation of high-performance pyrene-based photoresponsive materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973532","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}