Mohd Abdulla, Indrajith K. Biju, Ruchir Kant, Kishor Mohanan
{"title":"A Direct Additive-Free Route to Oxindole–Nitrones From α-Diazoacetamides and Nitrosoarenes","authors":"Mohd Abdulla, Indrajith K. Biju, Ruchir Kant, Kishor Mohanan","doi":"10.1002/ajoc.70564","DOIUrl":"https://doi.org/10.1002/ajoc.70564","url":null,"abstract":"<div>\u0000 \u0000 <p>A straightforward synthesis of (<i>E</i>)-oxindole–nitrones has been developed through the intramolecular cyclization of an in situ-generated acetamide–nitrone intermediate from the reaction of <i>α</i>-diazoacetamides with nitrosoarenes. The transformation proceeds under additive-free conditions in acetonitrile, exhibits a broad substrate scope, and furnishes the desired products in moderate to excellent yields.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Identification and Suppression of a dba-Derived Heck-Type Impurity in Negishi Coupling of 4-Iodopyridines","authors":"Yoshitaka Kitano, Mitsuhiro Arisawa","doi":"10.1002/ajoc.70561","DOIUrl":"https://doi.org/10.1002/ajoc.70561","url":null,"abstract":"<div>\u0000 \u0000 <p>During Negishi coupling of 4-iodopyridine derivatives with aryl zinc reagents using tris(dibenzylideneacetone)dipalladium (Pd<sub>2</sub>dba<sub>3</sub>), a previously overlooked dba-derived Heck-type impurity was identified and structurally characterized. Although trace impurities are tightly regulated in the manufacture of active pharmaceutical ingredients (APIs), their suppression is highly desirable. Systematic screening of palladium sources, ligands, and solvents revealed that a catalyst system generated from Pd<sub>2</sub>dba<sub>3</sub> and tricyclohexylphosphine (PCy<sub>3</sub>) effectively suppresses the formation of the dba-derived impurity while maintaining high coupling efficiency. Under the optimized conditions, a variety of 4-arylpyridine derivatives were synthesized in good to excellent yields, and the level of the dba-derived impurity was reduced below the threshold specified in The International Council for Harmonization of Technical Requirements for Pharmaceuticals for Human Use (ICH) guidelines. This study provides a practical Negishi coupling protocol for the synthesis of pharmaceutically relevant 4-arylpyridines with minimized catalyst-derived impurities.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149205401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"KI-Catalyzed Direct C-H Alkoxycarbonylation of Benzothiazoles With Glyoxylic Acid and Alcohols","authors":"Jing Guo, Wanqiang Wang, Ting Pang, Chuntian Li, Yonghong Liu, Ping Liu","doi":"10.1002/ajoc.70523","DOIUrl":"https://doi.org/10.1002/ajoc.70523","url":null,"abstract":"<div>\u0000 \u0000 <p>Herein, we report an efficient three-component alkoxycarbonylation for the direct synthesis of benzothiazole-2-carboxylates. Using benzothiazoles, glyoxylic acid monohydrate, and alcohols as starting materials, the synergistic KI/K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> catalytic system enables one-step ester construction. This method circumvents the need for prefunctionalized substrates and harsh reaction conditions, while allowing convenient tuning of the ester moiety through variation of the alcohol component. A broad range of substituted benzothiazoles and primary, secondary, and deuterated alcohols are well tolerated, demonstrating high functional group compatibility. Gram-scale experiments and subsequent product derivatization further underscore the synthetic utility of this protocol.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"HBr/DMSO-Mediated Oxidative Dehydrogenation of γ-Keto Sulfones to γ-Keto Vinyl Sulfones","authors":"Zhenlei Zhang, Wei Zhao, Manqi Zhang, Xiaozhen Li, Jun Yu, Jiaojiao Xu, Tianyou Zhang","doi":"10.1002/ajoc.70562","DOIUrl":"https://doi.org/10.1002/ajoc.70562","url":null,"abstract":"<div>\u0000 \u0000 <p>γ-Keto vinyl sulfones are valuable synthetic intermediates, yet efficient methods for their preparation remain limited. Herein, we report an HBr/DMSO-mediated oxidative dehydrogenation of γ-keto sulfones to γ-keto vinyl sulfones. This transition-metal-free protocol proceeds without external oxidants and features broad substrate scope and good functional-group tolerance. Mechanistic studies support an HBr-promoted enolization–bromination–dehydrobromination pathway. Further E/Z photoisomerization and bromination highlight the synthetic utility of the products.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Metal-Free Synthesis of Oxa Spiro-indene-1,3-dione Tetrahydrofurans and Pyrans via [3+2]/[4+2] Spirocyclization of 2-Arylidene-1,3-indanedione With Haloalcohols","authors":"Soni Jagdeve, Suresh Waghmode","doi":"10.1002/ajoc.70539","DOIUrl":"https://doi.org/10.1002/ajoc.70539","url":null,"abstract":"<div>\u0000 \u0000 <p>A concise and efficient method has been developed for the synthesis of pharmacologically important spiro-indene-1,3-dione- fused tetrahydrofurans and pyrans via a base-mediated cascade [3+2]/[4+2] spirocyclization of 2-arylidene-1,3-indandiones and 2-(3-phenylallylidene)-indandione with haloalcohols. This protocol offers several advantages, including a straightforward reaction process, short reaction times, broad substrate scope, high product yields, and mild, transition-metal-free reaction conditions. The practicality of this approach has been validated through gram-scale synthesis, which furnished the desired products in good yields.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Long-Jia Fan, Zi-Yan Wang, Ke-Xu Ren, Yi Hu, Hua-Jin Xu
{"title":"Catalytic-Amount Oxidant for Ester-Directed Pd-Catalyzed Olefination","authors":"Long-Jia Fan, Zi-Yan Wang, Ke-Xu Ren, Yi Hu, Hua-Jin Xu","doi":"10.1002/ajoc.70553","DOIUrl":"https://doi.org/10.1002/ajoc.70553","url":null,"abstract":"<div>\u0000 \u0000 <p>The development of cost-effective and efficient oxidation strategies employing catalytic amounts of oxidants, as alternatives to excessive and expensive metal–salt oxidants, remains highly significant in the field of organic synthesis. Herein, we report a weakly coordinating ester-directed Pd-catalyzed olefination enabled by catalytic amounts of oxidant, providing a cleaner and more practical strategy for synthetic applications. Desired yields could be obtained either by extending the reaction time or by adding an additional catalytic amount of Ag<sub>2</sub>CO<sub>3</sub>. This oxidation system not only successfully achieved gram-scale reaction amplification, but also significantly reduced the amount of palladium catalyst while maintaining high reaction efficiency.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Recent Advances in the Reaction of MBH Alcohols and Acetates: Scope and Mechanism (2016–2026)","authors":"Subhasis Samai, Sanghamitra Atta, Sukla Garain, Malkeet Singh, Maya Shankar Singh","doi":"10.1002/ajoc.70556","DOIUrl":"https://doi.org/10.1002/ajoc.70556","url":null,"abstract":"<div>\u0000 \u0000 <p>The Morita-Baylis-Hillman (MBH) reaction represents one of the economical and straightforward C─C bond-forming transformations in modern organic synthesis, yielding versatile polyfunctionalized products bearing electron-deficient alkenes with a hydroxy group at the allylic position. These products serve as valuable substrates for the development of new synthetic procedures for the synthesis of numerous natural products and biologically significant molecules. This review presents a comprehensive overview of transformations involving MBH alcohols and acetates reported during the past decade (2016–2026), covering both uncyclized and cyclized reactions, including C─C and C–heteroatom bond-forming processes. Recent developments in photocatalytic and metal-catalyzed transformations are also highlighted. Through a critical assessment of these advances, this review provides an up-to-date perspective on the expanding synthetic potential of MBH alcohols and acetates.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149084115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Organic Mixed-Valence π-Electron Systems—Current Status and Challenges","authors":"Akihiro Ito","doi":"10.1002/ajoc.70554","DOIUrl":"https://doi.org/10.1002/ajoc.70554","url":null,"abstract":"<p>Over the past few decades, our understanding of organic mixed-valence (MV) chemistry has advanced dramatically. During this period, the remarkable properties of MV states, arising from combinations of diverse π-bridging units and redox-active centers, have been elucidated. Currently, further progress is anticipated through sophisticated molecular design that utilizes the specific characteristics of each constituent unit. This review outlines the evolution of organic MV chemistry, discusses design principles, identifies unresolved challenges, and highlights emerging trends aimed at addressing them. Key areas of focus include deepening our understanding of the dynamic aspects of MV states (including molecular vibrations), developing novel MV systems by effectively utilizing both intramolecular and intermolecular MV states, and the molecular design, development, and characterization of multi-redox-centered MV multi-radical systems.</p>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.70554","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149084154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Caterina Campinoti, Lukas Andru, Simona Marchetti, Mauro Pineschi, Fabio Bellina, Antonio Del Vecchio, Marco Lessi
{"title":"Mechanochemical Synthesis and Functionalization of Oxadiazo[2.2.2]octenes Through Oxidative Nitroso Diels–Alder Reaction and Hetero-Cope Rearrangement","authors":"Caterina Campinoti, Lukas Andru, Simona Marchetti, Mauro Pineschi, Fabio Bellina, Antonio Del Vecchio, Marco Lessi","doi":"10.1002/ajoc.70557","DOIUrl":"https://doi.org/10.1002/ajoc.70557","url":null,"abstract":"<div>\u0000 \u0000 <p>The present work reports a straightforward approach for the mechanochemical oxidative nitroso Diels–Alder (DA) reaction for the rapid synthesis of oxadiazo[2.2.2]octenes and a mechanochemical [3+3] hetero-Cope rearrangement to access the corresponding dioxazines within reduced reaction time (up to 1.5 min and 1.5 h, respectively), high yields and reproducibility toward different functional groups.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149084152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthetic Approaches to Selenophosphates and Tellurophosphates","authors":"Xin Li, Changjiang Wu, Gong-Qing Liu","doi":"10.1002/ajoc.70559","DOIUrl":"https://doi.org/10.1002/ajoc.70559","url":null,"abstract":"<div>\u0000 \u0000 <p>Organoselenophosphates and tellurophosphates represent important structural motifs in organochalcogenophosphorus chemistry and exhibit unique electronic properties, distinctive biological activities, and versatile synthetic utility. This review provides a systematic overview of recent methodological advances in the synthesis of these two classes of compounds, with particular emphasis on the mechanistic features of key transformations. For selenophosphates, the synthetic strategies are categorized into seven classes based on the selenium source employed: selenohalides, selenophthalimides, selenocyanates, selenols, selenosulfonates, elemental selenium powder, and diselenides. The reaction characteristics and substrate scope of each approach are discussed in detail. In contrast, synthetic methods for tellurophosphates remain considerably less developed, primarily because of the inherent instability of P–Te bonds between air, moisture, and light. The available protocols for tellurophosphate construction are also comprehensively reviewed. Finally, future challenges and opportunities in this field are highlighted, including catalytic selenium/tellurium recycling, asymmetric synthesis, stability enhancement, and applications against drug-resistant bacteria, with the aim of providing reference and inspiration for further research in this underexplored area.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149084151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}