Nandini B. Kale , Mary Sravani Galla , Nagula Shankaraiah
Functionalized alkynes have emerged as pivotal entities in modern synthetic chemistry and also exhibit as versatile building blocks toward the construction of diverse molecular frameworks. This review emphasizes a comprehensive overview of recent advancements in the applications of functionalized alkynes, such as ynals, ynamides, alkynols, diynes, and miscellaneous alkynes in annulation reactions. The review also discussed the utility of functionalized alkynes from traditional organic synthesis to innovative metal‐mediated transformations, late‐stage functionalization of complex molecules, medicinal chemistry, including natural products and pharmaceuticals.
{"title":"Harnessing Functionalized Alkynes in Annulation Reactions: A Comprehensive Review","authors":"Nandini B. Kale , Mary Sravani Galla , Nagula Shankaraiah","doi":"10.1002/ajoc.70290","DOIUrl":"10.1002/ajoc.70290","url":null,"abstract":"<div><div>Functionalized alkynes have emerged as pivotal entities in modern synthetic chemistry and also exhibit as versatile building blocks toward the construction of diverse molecular frameworks. This review emphasizes a comprehensive overview of recent advancements in the applications of functionalized alkynes, such as ynals, ynamides, alkynols, diynes, and miscellaneous alkynes in annulation reactions. The review also discussed the utility of functionalized alkynes from traditional organic synthesis to innovative metal‐mediated transformations, late‐stage functionalization of complex molecules, medicinal chemistry, including natural products and pharmaceuticals.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70290"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887722","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}
Wei Wang , Rongrong Li , Yuexiu Cao , Li Wang , Jinying Cao , Peng Qian , Yannan Zhu
A base‐promoted [4+2] annulation reaction between indole‐2‐carboxamides and vinylsulfonium salts has been developed, affording the pyrazinoindolones in 39%–96% yields with high chemoselectivity. The synthesis strategy of vinylsulfonium salts can also approach to benzimidazole‐fused azabicyclo[3.1.0]hexanes via a [3+2]/[2+1] annulation process with benzimidazole‐derived acrylonitriles as the reaction partners.
{"title":"[4+2] Annulation Reaction of Indole‐2‐Carboxamides With Vinylsulfonium Salts: Synthesis of Pyrazinoindolones","authors":"Wei Wang , Rongrong Li , Yuexiu Cao , Li Wang , Jinying Cao , Peng Qian , Yannan Zhu","doi":"10.1002/ajoc.70304","DOIUrl":"10.1002/ajoc.70304","url":null,"abstract":"<div><div>A base‐promoted [4+2] annulation reaction between indole‐2‐carboxamides and vinylsulfonium salts has been developed, affording the pyrazinoindolones in 39%–96% yields with high chemoselectivity. The synthesis strategy of vinylsulfonium salts can also approach to benzimidazole‐fused azabicyclo[3.1.0]hexanes via a [3+2]/[2+1] annulation process with benzimidazole‐derived acrylonitriles as the reaction partners.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70304"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146091401","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}
Hiren Jungi , Sumana Podder , Dheeraj Kumar , R. S. Malavika , Rositha Kuniyil , Joyee Mitra
Knoevenagel condensation reaction is a crucial C─C bond formation reaction in organic synthesis, providing access to diverse biological and industrial intermediates. Although catalyst‐free protocols for this reaction have been explored, they often suffer from sluggish kinetics and limited substrate scope, typically restricted to aromatic aldehydes. Herein, we explore a family of basic ionic liquids (ILs) synthesized from naturally occurring pyridine carboxylic acid as an organocatalyst for Knoevenagel condensation. The presence of a carboxylate group adjacent to pyridine in the catalyst significantly enhances its efficiency, enabling solvent‐free reactions under mild conditions, with ultralow IL loadings (∼ 0.2 mol%). DFT calculations revealed that the pyridine‐assisted pathway is energetically favorable compared to the carboxylate‐mediated route. The designed system is an efficient and reusable organocatalyst for Knoevenagel condensation, catering to a broad substrate scope including aromatic, heterocyclic, and less electrophilic aliphatic aldehydes. Moreover, this protocol enables the green synthesis of bioactive tetrahydrobenzo[b]pyrans via a one‐pot, three‐component reaction. Calculated green metrics further validated the practical applicability of the catalytic protocol, toward the sustainable production of industrially relevant molecules, as the calculated E‐factor value of 0.16 aligns with reported IL‐based green protocols.
{"title":"Experimental and Computational Study of Pyridine Carboxylate Ionic Liquid‐Mediated Knoevenagel Condensation at Ultralow Loadings","authors":"Hiren Jungi , Sumana Podder , Dheeraj Kumar , R. S. Malavika , Rositha Kuniyil , Joyee Mitra","doi":"10.1002/ajoc.202500635","DOIUrl":"10.1002/ajoc.202500635","url":null,"abstract":"<div><div>Knoevenagel condensation reaction is a crucial C─C bond formation reaction in organic synthesis, providing access to diverse biological and industrial intermediates. Although catalyst‐free protocols for this reaction have been explored, they often suffer from sluggish kinetics and limited substrate scope, typically restricted to aromatic aldehydes. Herein, we explore a family of basic ionic liquids (ILs) synthesized from naturally occurring pyridine carboxylic acid as an organocatalyst for Knoevenagel condensation. The presence of a carboxylate group adjacent to pyridine in the catalyst significantly enhances its efficiency, enabling solvent‐free reactions under mild conditions, with ultralow IL loadings (∼ 0.2 mol%). DFT calculations revealed that the pyridine‐assisted pathway is energetically favorable compared to the carboxylate‐mediated route. The designed system is an efficient and reusable organocatalyst for Knoevenagel condensation, catering to a broad substrate scope including aromatic, heterocyclic, and less electrophilic aliphatic aldehydes. Moreover, this protocol enables the green synthesis of bioactive tetrahydrobenzo[b]pyrans via a one‐pot, three‐component reaction. Calculated green metrics further validated the practical applicability of the catalytic protocol, toward the sustainable production of industrially relevant molecules, as the calculated <em>E</em>‐factor value of 0.16 aligns with reported IL‐based green protocols.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e00635"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098543","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}
A practical and efficient potassium trimethylsilanolate/nitrile system for constructing all‐carbon quaternary centers has been developed. This transition‐metal free protocol utilizes readily available chlorides and 1,3‐dicarbonyl compounds, enabling the selective formation of two C─C bonds in a single operation. The reaction features broad substrate scope, good functional group tolerance, large scale synthesis, and further structural modification, providing a mild approach to access quaternary centers in moderate to excellent yields.
{"title":"Transition‐Metal Free Dialkylation to Construct All‐Carbon Quaternary Centers From Alkyl Chlorides and 1,3‐Dicarbonyl Compounds","authors":"Wenjing Liu , Feng Zhao","doi":"10.1002/ajoc.70276","DOIUrl":"10.1002/ajoc.70276","url":null,"abstract":"<div><div>A practical and efficient potassium trimethylsilanolate/nitrile system for constructing all‐carbon quaternary centers has been developed. This transition‐metal free protocol utilizes readily available chlorides and 1,3‐dicarbonyl compounds, enabling the selective formation of two C─C bonds in a single operation. The reaction features broad substrate scope, good functional group tolerance, large scale synthesis, and further structural modification, providing a mild approach to access quaternary centers in moderate to excellent yields.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70276"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145891455","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}
Dandan Zhao , Hongyan Yang , Xiaoli Wang , Peng He , Yanli Xu , Qifu Lin
A highly efficient iridium‐catalyzed ring‐opening reactions of heterobicyclic alkenes with fluoroalkyl alcohols has been developed. The reaction utilizes readily available fluoroalkyl alcohols as fluoroalkoxylation reagents and exhibits a wide substrate scope, affording the fluoroalkoxylated products with trans‐1,2‐disubstituted dihydronaphthalene framework in good to excellent yields. Mechanistic insights, supported by computational studies, have been proposed to elucidate the reaction pathway.
{"title":"Iridium‐Catalyzed Anti‐Stereoselective Ring‐Opening Fluoroalkoxylation of Heterobicyclic Alkenes","authors":"Dandan Zhao , Hongyan Yang , Xiaoli Wang , Peng He , Yanli Xu , Qifu Lin","doi":"10.1002/ajoc.70274","DOIUrl":"10.1002/ajoc.70274","url":null,"abstract":"<div><div>A highly efficient iridium‐catalyzed ring‐opening reactions of heterobicyclic alkenes with fluoroalkyl alcohols has been developed. The reaction utilizes readily available fluoroalkyl alcohols as fluoroalkoxylation reagents and exhibits a wide substrate scope, affording the fluoroalkoxylated products with <em>trans</em>‐1,2‐disubstituted dihydronaphthalene framework in good to excellent yields. Mechanistic insights, supported by computational studies, have been proposed to elucidate the reaction pathway.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70274"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145891121","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}
Shiyun Li , Yan An , Lulu Wang , Xin Li , Yao Tan , Bin Wen , Tiesen Li , Xingquan Chen
A highly efficient electrochemical oxidative dehydrogenative N–N coupling of arylamines to selectively provide benzo[c]cinnolines and azoarenes has been investigated. In this simple process, various functional groups were tolerated under mild reaction conditions without additional metal or oxidant, and the practicality of the protocol was demonstrated by the preparation of benzo[c]cinnolines on a gram scale and later derivatization. Mechanism of studies shows that the reaction proceeds via a radical pathway with the hydrazine compound as an intermediate. Additionally, the base plays an important role in this transformation, potentially facilitating the dehydrogenation process.
{"title":"Electrochemical Oxidative N–N Coupling to Construct Benzo[c]cinnolines and Azoarenes","authors":"Shiyun Li , Yan An , Lulu Wang , Xin Li , Yao Tan , Bin Wen , Tiesen Li , Xingquan Chen","doi":"10.1002/ajoc.70271","DOIUrl":"10.1002/ajoc.70271","url":null,"abstract":"<div><div>A highly efficient electrochemical oxidative dehydrogenative N–N coupling of arylamines to selectively provide benzo[<em>c</em>]cinnolines and azoarenes has been investigated. In this simple process, various functional groups were tolerated under mild reaction conditions without additional metal or oxidant, and the practicality of the protocol was demonstrated by the preparation of benzo[<em>c</em>]cinnolines on a gram scale and later derivatization. Mechanism of studies shows that the reaction proceeds via a radical pathway with the hydrazine compound as an intermediate. Additionally, the base plays an important role in this transformation, potentially facilitating the dehydrogenation process.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70271"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887828","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}
Divya Shrestha , Karuna Mahato , Prasanta Roy , Seung Woo Lee , Yong Rok Lee
Maleimide‐containing molecules serve as important scaffolds for biological activities as well as photochemical properties and play a significant role in both the academic and industrial communities. Maleimides are versatile coupling partners owing to their diverse reactivities with transition‐metal catalysts in C–H activation and annulation reactions including alkenylation, alkylation, fused‐annulation, and spiro‐annulation for the synthesis of numerous maleimide‐containing bioactive molecules such as succinamides, lactams, and lactims. In this review, innovative advances toward the synthesis of biologically important maleimide/succinimide‐bearing scaffolds through C–H activation and annulation reactions with transition metal as catalysts, with particular emphasis on the intermediates, transition states, and incorporation of different annulation sites for maleimide is reviewed. This review covers research published between 2019 and 2025, highlighting the substrate scope, reaction mechanisms, synthetic transformations, and future prospects of this approach.
{"title":"Maleimides as Versatile Reactive Platforms in Transition‐Metal‐Catalyzed C–H Activation/Annulation","authors":"Divya Shrestha , Karuna Mahato , Prasanta Roy , Seung Woo Lee , Yong Rok Lee","doi":"10.1002/ajoc.70294","DOIUrl":"10.1002/ajoc.70294","url":null,"abstract":"<div><div>Maleimide‐containing molecules serve as important scaffolds for biological activities as well as photochemical properties and play a significant role in both the academic and industrial communities. Maleimides are versatile coupling partners owing to their diverse reactivities with transition‐metal catalysts in C–H activation and annulation reactions including alkenylation, alkylation, fused‐annulation, and spiro‐annulation for the synthesis of numerous maleimide‐containing bioactive molecules such as succinamides, lactams, and lactims. In this review, innovative advances toward the synthesis of biologically important maleimide/succinimide‐bearing scaffolds through C–H activation and annulation reactions with transition metal as catalysts, with particular emphasis on the intermediates, transition states, and incorporation of different annulation sites for maleimide is reviewed. This review covers research published between 2019 and 2025, highlighting the substrate scope, reaction mechanisms, synthetic transformations, and future prospects of this approach.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70294"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145983614","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}
Xuehua Zhang , Jie Gao , Binyu He , Mengtian Dong , Tiankai Zhang , Jun Dong , Feng Chen
This work presents a visible‐light‐driven annulation protocol for synthesizing 6‐silylphenanthridines from 2‐isocyanobiaryls and silanes using mesoporous graphitic carbon nitride (mpg‐CN) as a heterogeneous photocatalyst. The mpg‐CN catalyst demonstrates exceptional recyclability, maintaining consistent activity over five consecutive cycles without loss of performance. Operating under ambient conditions without requiring precious metals or expensive organic photo redox catalysts, this method offers mild reaction conditions, cost efficiency, and operational simplicity. The protocol provides a scalable and sustainable approach to accessing 6‐silyl‐substituted phenanthridines, highlighting the potential of heterogeneous photocatalysis in organic synthesis.
{"title":"mpg‐CN Photo‐Catalyzed Annulation of 2‑Isocyanobiaryls With Silanes to 6‑Silyl‐Substituted Phenanthridines","authors":"Xuehua Zhang , Jie Gao , Binyu He , Mengtian Dong , Tiankai Zhang , Jun Dong , Feng Chen","doi":"10.1002/ajoc.70299","DOIUrl":"10.1002/ajoc.70299","url":null,"abstract":"<div><div>This work presents a visible‐light‐driven annulation protocol for synthesizing 6‐silylphenanthridines from 2‐isocyanobiaryls and silanes using mesoporous graphitic carbon nitride (mpg‐CN) as a heterogeneous photocatalyst. The mpg‐CN catalyst demonstrates exceptional recyclability, maintaining consistent activity over five consecutive cycles without loss of performance. Operating under ambient conditions without requiring precious metals or expensive organic photo redox catalysts, this method offers mild reaction conditions, cost efficiency, and operational simplicity. The protocol provides a scalable and sustainable approach to accessing 6‐silyl‐substituted phenanthridines, highlighting the potential of heterogeneous photocatalysis in organic synthesis.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70299"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146002062","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}
Optically active 2‐azatriptycene 1 bearing a 1‐pyrenyl unit was synthesized. The resolved enantiomers exhibited blue circularly polarized luminescence (CPL) in solution, with dissymmetry factor glum on the order of 10−4–10−5. In contrast, the corresponding protonated species 1H+ exhibited green CPL with reversed sign, demonstrating that optically active 2‐azatriptycene functions as an acid‐responsive chiral switching unit.
{"title":"Optically Active 2‐Azatriptycene Bearing a 1‐Pyrenyl Unit Exhibiting Acid‐Induced CPL Switching With Sign Inversion","authors":"Yusuke Hashimoto , Ryo Inoue , Masayuki Gon , Kazuo Tanaka , Norihiro Aiga , Satoshi Takeuchi , Kazuya Kubo , Tomohiro Agou","doi":"10.1002/ajoc.70297","DOIUrl":"10.1002/ajoc.70297","url":null,"abstract":"<div><div>Optically active 2‐azatriptycene <strong>1</strong> bearing a 1‐pyrenyl unit was synthesized. The resolved enantiomers exhibited blue circularly polarized luminescence (CPL) in solution, with dissymmetry factor <em>g</em><sub>lum</sub> on the order of 10<sup>−4</sup>–10<sup>−5</sup><sub>.</sub> In contrast, the corresponding protonated species <strong>1H</strong><sup>+</sup> exhibited green CPL with reversed sign, demonstrating that optically active 2‐azatriptycene functions as an acid‐responsive chiral switching unit.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70297"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146002342","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}
Yatharth Joshi , Manorama Singh , Ankita Rai , Vijai K. Rai
The organic compounds containing guanidine moieties are known to show several applications in the field of medicines, catalysts, and polymers, etc. The use of guanidines has been explored by researchers all over the world. Guanidines serve as an important tool in the synthesis of heterocycles, which serve as therapeutic agents and also show a wide array of applications. Due to their cost efficiency, atom economy, and eco‐friendliness, Multicomponent reactions (MCRs) have drawn the attention of researchers and scientists all over the world. This review highlights the applications of guanidines as a reagent as well as a catalyst in synthesizing various heterocyclic scaffolds via one‐pot Multicomponent reactions.
{"title":"Y‐Aromatic Guanidines as Steering Reagent in Multicomponent Heterocyclic Syntheses","authors":"Yatharth Joshi , Manorama Singh , Ankita Rai , Vijai K. Rai","doi":"10.1002/ajoc.70311","DOIUrl":"10.1002/ajoc.70311","url":null,"abstract":"<div><div>The organic compounds containing guanidine moieties are known to show several applications in the field of medicines, catalysts, and polymers, etc. The use of guanidines has been explored by researchers all over the world. Guanidines serve as an important tool in the synthesis of heterocycles, which serve as therapeutic agents and also show a wide array of applications. Due to their cost efficiency, atom economy, and eco‐friendliness, Multicomponent reactions (MCRs) have drawn the attention of researchers and scientists all over the world. This review highlights the applications of guanidines as a reagent as well as a catalyst in synthesizing various heterocyclic scaffolds via one‐pot Multicomponent reactions.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70311"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146049386","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}