Yi‐Jiang Guo , Zhao‐Yan Fu , Ai‐Rong She , Fei Wang , Chi‐Xian He , Teng Liu
Nitrogen‐containing heterocycles are widely distributed in realm of natural products, pharmaceuticals, and function materials. Compared to the traditional batch synthesis, continuous‐flow technology emerges as a transformative platform with multiple advantages, such as enhanced mass/heat transfer, precise temperature control, continuous large‐scale production, minimizing the need for intermediate separation and purification, and safe operation etc. Based on the continuous‐flow strategies, this review systematically evaluates recent advances for the synthesis of nitrogen‐containing heterocycles through sequence transformations in the past decade (2016–2025), including three‐, four‐, five‐, six‐, seven‐membered ring. Furthermore, in combination with heterogeneous catalysis, photocatalysis, electrocatalysis, or microwave radiation etc., the continuous‐flow technology greatly enriches the organic synthesis pathways and produces diversified nitrogen‐containing heterocycles and related pharmaceuticals.
{"title":"Advances in Continuous‐Flow Synthesis of Nitrogen‐Containing Heterocycles Through Sequence Transformations in the Past Decade (2016–2025)","authors":"Yi‐Jiang Guo , Zhao‐Yan Fu , Ai‐Rong She , Fei Wang , Chi‐Xian He , Teng Liu","doi":"10.1002/ajoc.202500614","DOIUrl":"10.1002/ajoc.202500614","url":null,"abstract":"<div><div>Nitrogen‐containing heterocycles are widely distributed in realm of natural products, pharmaceuticals, and function materials. Compared to the traditional batch synthesis, continuous‐flow technology emerges as a transformative platform with multiple advantages, such as enhanced mass/heat transfer, precise temperature control, continuous large‐scale production, minimizing the need for intermediate separation and purification, and safe operation etc. Based on the continuous‐flow strategies, this review systematically evaluates recent advances for the synthesis of nitrogen‐containing heterocycles through sequence transformations in the past decade (2016–2025), including three‐, four‐, five‐, six‐, seven‐membered ring. Furthermore, in combination with heterogeneous catalysis, photocatalysis, electrocatalysis, or microwave radiation etc., the continuous‐flow technology greatly enriches the organic synthesis pathways and produces diversified nitrogen‐containing heterocycles and related pharmaceuticals.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00614"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501051","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}
Elisavet‐Maria Zantioti‐Chatzouda , Stavroula‐Aikaterini Kaplani , Eleni‐Maria Stroda , Prof. Dr. Nikolaos Eleftheriadis , Prof. Dr. Manolis Stratakis
Cs2CO3 or CF3COOAg catalyze the intramolecular 6‐endo hydroamination of the Z‐enaminones derived from the Michael‐type addition of primary amines to skipped diynones, yielding N‐substituted 4‐pyridones in good to excellent yields. The transformation occurs in one‐pot operation, with the first step being noncatalyzed. While the Cs2CO3‐catalyzed protocol is much faster, it fails to provide significant yields in the case of enaminones derived from aryl‐substituted diynones. On the other hand, the Ag(I)‐catalyzed one is a slower process but more widely applicable. Several N‐substituted 4‐pyridones inhibit SecA ATPase at micromolar concentrations.
{"title":"Synthesis of N‐Substituted 4‐Pyridones From Skipped Diynones via Intramolecular Base or Ag(I)‐Catalyzed Hydroamination","authors":"Elisavet‐Maria Zantioti‐Chatzouda , Stavroula‐Aikaterini Kaplani , Eleni‐Maria Stroda , Prof. Dr. Nikolaos Eleftheriadis , Prof. Dr. Manolis Stratakis","doi":"10.1002/ajoc.202500608","DOIUrl":"10.1002/ajoc.202500608","url":null,"abstract":"<div><div>Cs<sub>2</sub>CO<sub>3</sub> or CF<sub>3</sub>COOAg catalyze the intramolecular 6‐endo hydroamination of the Z‐enaminones derived from the Michael‐type addition of primary amines to skipped diynones, yielding N‐substituted 4‐pyridones in good to excellent yields. The transformation occurs in one‐pot operation, with the first step being noncatalyzed. While the Cs<sub>2</sub>CO<sub>3</sub>‐catalyzed protocol is much faster, it fails to provide significant yields in the case of enaminones derived from aryl‐substituted diynones. On the other hand, the Ag(I)‐catalyzed one is a slower process but more widely applicable. Several N‐substituted 4‐pyridones inhibit SecA ATPase at micromolar concentrations.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00608"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501057","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}
Dr Sheela Kumari , Dr Ankur Maji , Rahul Chauhan , Virendra Kumar Chaudhary , Rahul Saini , Dr U. P. Singh , Dr Kaushik Ghosh
Cu(II) complexes were synthesized via intramolecular hydroxylation utilizing hydrogen peroxide, mimicking the structure and action of the catechol oxidase enzyme. Utilizing these complexes, multicomponent reaction was established to produce benzoxazole derivatives. This reaction involved the combination of catechol with either an aldehyde or alcohol in the presence of ammonium acetate, serving as the nitrogen provider. Multiple control experiments were conducted to clarify the underlying mechanism. The utility of this approach was showcased through the large‐scale synthesis of several benzoxazole derivatives.
{"title":"Sustainable Multicomponent Synthesis of Benzoxazoles from Alcohols and Aldehydes Catalyzed by Copper Catalysts","authors":"Dr Sheela Kumari , Dr Ankur Maji , Rahul Chauhan , Virendra Kumar Chaudhary , Rahul Saini , Dr U. P. Singh , Dr Kaushik Ghosh","doi":"10.1002/ajoc.202500572","DOIUrl":"10.1002/ajoc.202500572","url":null,"abstract":"<div><div>Cu(II) complexes were synthesized via intramolecular hydroxylation utilizing hydrogen peroxide, mimicking the structure and action of the catechol oxidase enzyme. Utilizing these complexes, multicomponent reaction was established to produce benzoxazole derivatives. This reaction involved the combination of catechol with either an aldehyde or alcohol in the presence of ammonium acetate, serving as the nitrogen provider. Multiple control experiments were conducted to clarify the underlying mechanism. The utility of this approach was showcased through the large‐scale synthesis of several benzoxazole derivatives.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00572"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501112","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}
The detection of chemical warfare agents (CWAs) through simple and rapid methods with real‐sample applicability is crucial for reducing the risks they pose to living systems during unexpected terror attacks and armed conflicts. In response, there is growing demand for portable, wearable, and lightweight badge‐based kits that enable safe, user‐friendly, and on‐site detection of chemical warfare agents. For this purpose, we have developed a rhodamine‐based system incorporating a 2,6‐diaminopyridine probe (APX) with single X‐ray structure proof, enabling the visual detection of the Sarin simulant, diethyl chlorophosphate (DCP), in both solution and vapor phases. Three model compounds (MPX, AmPhX, and MeOPhX) were synthesized. Interestingly, upon reacting with DCP in acetonitrile, APX and MPX showed a distinct fluorescence turn‐on response at 582 nm, featuring an instantaneous reaction for probe APX (< 5 s) with a detection limit (2.5 nM), which is below the threshold level. The nucleophilicity of the pyridine‐N atom is influenced by the electron donating ability of 2‐amino group, which affects the intramolecular charge‐transfer (ICT) in the reaction site, resulting in a very fast reaction with DCP. The reaction‐based sensing mechanism was validated through high‐resolution mass spectrometry (HRMS) and nuclear magnetic resonance (1H NMR and 31P NMR) spectroscopy. Finally, the probe APX has been used to develop a test‐strip and badge‐based portable system for real‐time on‐site monitoring of DCP, enabling simple, safe, and selective detection.
{"title":"Fluorescent Chemosensors With Varying Degrees of Nucleophilicity for the Fast Detection of a Chemical Warfare Agent Mimic: Development of a Polymer Film Badge for On‐Site Detection","authors":"Pintu Ghosh , Loknath Pakhira , Abhishek Manna , Dipanjan Banik , Souvik Bisui , Debasish Mandal , Ajit Kumar Mahapatra","doi":"10.1002/ajoc.202500611","DOIUrl":"10.1002/ajoc.202500611","url":null,"abstract":"<div><div>The detection of chemical warfare agents (CWAs) through simple and rapid methods with real‐sample applicability is crucial for reducing the risks they pose to living systems during unexpected terror attacks and armed conflicts. In response, there is growing demand for portable, wearable, and lightweight badge‐based kits that enable safe, user‐friendly, and on‐site detection of chemical warfare agents. For this purpose, we have developed a rhodamine‐based system incorporating a 2,6‐diaminopyridine probe (APX) with single X‐ray structure proof, enabling the visual detection of the Sarin simulant, diethyl chlorophosphate (DCP), in both solution and vapor phases. Three model compounds (MPX, AmPhX, and MeOPhX) were synthesized. Interestingly, upon reacting with DCP in acetonitrile, APX and MPX showed a distinct fluorescence turn‐on response at 582 nm, featuring an instantaneous reaction for probe APX (< 5 s) with a detection limit (2.5 nM), which is below the threshold level. The nucleophilicity of the pyridine‐N atom is influenced by the electron donating ability of 2‐amino group, which affects the intramolecular charge‐transfer (ICT) in the reaction site, resulting in a very fast reaction with DCP. The reaction‐based sensing mechanism was validated through high‐resolution mass spectrometry (HRMS) and nuclear magnetic resonance (<sup>1</sup>H NMR and <sup>31</sup>P NMR) spectroscopy. Finally, the probe APX has been used to develop a test‐strip and badge‐based portable system for real‐time on‐site monitoring of DCP, enabling simple, safe, and selective detection.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00611"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500873","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 variety of N‐heterocyclic derivatives were synthesized by iodine‐mediated aminative difunctionalization/cyclization of N‐alkenyl sulfonamides. The present synthetic process involves nitrogen‐centered radicals generated from sulfonamide precursors. It is operationally simple and amenable to gram‐scale synthesis under transition‐metal‐free conditions. The reaction is applicable to the synthesis of iodinated N‐heterocyclic products in the absence of disulfides/diselenides and also to the preparation of thiolated/selenylated products in their presence, respectively.
{"title":"Iodine‐Mediated Difunctionalization/Cyclization of N‐Alkenyl Sulfonamides to Access N‐Heterocyclic Derivatives","authors":"Huilin Qiu , Kaituo Du , Zhiying Lun , Junbiao Chang , Wenquan Yu","doi":"10.1002/ajoc.70180","DOIUrl":"10.1002/ajoc.70180","url":null,"abstract":"<div><div>A variety of N‐heterocyclic derivatives were synthesized by iodine‐mediated aminative difunctionalization/cyclization of <em>N</em>‐alkenyl sulfonamides. The present synthetic process involves nitrogen‐centered radicals generated from sulfonamide precursors. It is operationally simple and amenable to gram‐scale synthesis under transition‐metal‐free conditions. The reaction is applicable to the synthesis of iodinated N‐heterocyclic products in the absence of disulfides/diselenides and also to the preparation of thiolated/selenylated products in their presence, respectively.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70180"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500887","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}
Jin‐Ping Li , Zhi‐Jing Guo , Jun‐Feng Wang , Li‐Sheng Wang , Jun Jiang , Hong‐Liang Li
This study presents an efficient method for synthesizing triaryl‐substituted acyclic olefins, employing palladium‐catalyzed diarylation of primary C(sp3)─H bonds at the γ‐position of 2‐(2‐phenylpropyl)pyridine derivatives, using halogen‐substituted aryl boronic esters as coupling reagents. Intramolecular β‐hydride elimination plays a key role in facilitating the formation of these compounds. The diarylation reaction proceeds smoothly with high functional group tolerance and good yields, even on a gram scale. Preliminary mechanistic studies suggest that the reaction may proceed through a Pd(II)/Pd(IV) catalytic cycle. This approach offers a novel strategy for the one‐pot synthesis of triaryl‐substituted acyclic olefin derivatives.
{"title":"Synthesis of Triaryl‐Substituted Acyclic Olefins via Palladium‐Catalyzed γ‐C(sp3)‐H Diarylation of 2‐(2‐Phenylpropyl)pyridine Derivatives","authors":"Jin‐Ping Li , Zhi‐Jing Guo , Jun‐Feng Wang , Li‐Sheng Wang , Jun Jiang , Hong‐Liang Li","doi":"10.1002/ajoc.202500564","DOIUrl":"10.1002/ajoc.202500564","url":null,"abstract":"<div><div>This study presents an efficient method for synthesizing triaryl‐substituted acyclic olefins, employing palladium‐catalyzed diarylation of primary C(sp<sup>3</sup>)─H bonds at the γ‐position of 2‐(2‐phenylpropyl)pyridine derivatives, using halogen‐substituted aryl boronic esters as coupling reagents. Intramolecular β‐hydride elimination plays a key role in facilitating the formation of these compounds. The diarylation reaction proceeds smoothly with high functional group tolerance and good yields, even on a gram scale. Preliminary mechanistic studies suggest that the reaction may proceed through a Pd(II)/Pd(IV) catalytic cycle. This approach offers a novel strategy for the one‐pot synthesis of triaryl‐substituted acyclic olefin derivatives.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00564"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501047","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}
Fengjuan Jia , Donghui Ding , Qing Gao , Yanping Zhang , Yichen Tao , Prof. Dr. Qiuju Zhou , Prof. Dr. Lin Tang
We report a practical photochemical approach for alkene difluoroalkylacylation using easily available 2‐(allyloxy)arylaldehydes and bromodifluoroacetates (or bromodifluoroacetamides). This method features broad substrate scope and enables the efficient synthesis of various valuable RCF2‐functionalized chroman‐4‐ones at room temperature. Key mechanistic insights show that the bifunctional bromodifluoroacetates (or bromodifluoroacetamides) act as both difluoroalkyl source and hydrogen atom acceptor. Consequently, the visible light‐driven difunctionalization of alkenes successfully proceeds without the need for external photocatalysts.
{"title":"Visible Light‐Promoted Catalyst‐Free Difluoroalkylacylation of Alkenes Toward RCF2‐Functionalized Chroman‐4‐ones","authors":"Fengjuan Jia , Donghui Ding , Qing Gao , Yanping Zhang , Yichen Tao , Prof. Dr. Qiuju Zhou , Prof. Dr. Lin Tang","doi":"10.1002/ajoc.70192","DOIUrl":"10.1002/ajoc.70192","url":null,"abstract":"<div><div>We report a practical photochemical approach for alkene difluoroalkylacylation using easily available 2‐(allyloxy)arylaldehydes and bromodifluoroacetates (or bromodifluoroacetamides). This method features broad substrate scope and enables the efficient synthesis of various valuable RCF<sub>2</sub>‐functionalized chroman‐4‐ones at room temperature. Key mechanistic insights show that the bifunctional bromodifluoroacetates (or bromodifluoroacetamides) act as both difluoroalkyl source and hydrogen atom acceptor. Consequently, the visible light‐driven difunctionalization of alkenes successfully proceeds without the need for external photocatalysts.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70192"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500796","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}
Wenjun Luo , Yan‐Xin Peng , Zu‐Qin Mei , De‐Liang Chen , Xiao‐Mei Cao , Prof. Dr. Yong Zhang
We describe herein the catalytic strategy to generate difluoroenolates from difluoroisoxazolacetophenone (DFIO) for C─C bond formation, allowing for the development of the organocatalytic difluoroalkylation of N‐aryl tetrahydroisoquinoline. The reaction is performed in the absence of chemical oxidants under mild conditions and only requires organic base as a catalyst and molecular oxygen as an oxidant. In addition, this protocol provides a new and convenient approach for the synthesis of compounds containing α,α‐difluoroketone motif.
{"title":"Organocatalytic Direct Csp3−H Difluoroalkylation of N‐Aryltetrahydroisoquinoline","authors":"Wenjun Luo , Yan‐Xin Peng , Zu‐Qin Mei , De‐Liang Chen , Xiao‐Mei Cao , Prof. Dr. Yong Zhang","doi":"10.1002/ajoc.202500547","DOIUrl":"10.1002/ajoc.202500547","url":null,"abstract":"<div><div>We describe herein the catalytic strategy to generate difluoroenolates from difluoroisoxazolacetophenone (DFIO) for C─C bond formation, allowing for the development of the organocatalytic difluoroalkylation of <em>N</em>‐aryl tetrahydroisoquinoline. The reaction is performed in the absence of chemical oxidants under mild conditions and only requires organic base as a catalyst and molecular oxygen as an oxidant. In addition, this protocol provides a new and convenient approach for the synthesis of compounds containing <em>α</em>,<em>α</em>‐difluoroketone motif.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00547"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500842","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}
Hui‐Ying Ren , Miao Wang , Shan Jiang , Yang‐Yang Zhou , Zi‐Xiang Lu , Cheng Xu , Bang‐Tun Zhao
Imidazo[1,2‐a]pyridine represents a significant heterocyclic scaffold, and its C3‐aminated derivatives demonstrate enhanced bioactivity. However, employing primary arylamines directly as aminating agents remains challenging to date. Herein, we report the PIDA‐enabled C3‐amination of imidazopyridines employing primary aromatic amines as the amination reagents, with rongalite as an in situ C1‐building block. This approach addresses the substrate scope limitations in C3‐amination reactions of imidazopyridines using primary aromatic amines. Mechanistic investigations have demonstrated that rongalite serves as a reactive C1 synthon, initially enabling C3‐aminomethylation of imidazopyridines with primary aromatic amines, followed by PIDA‐enabled 1,2‐ipso‐migration to achieve C3‐amination. This C3‐amination protocol is highly efficient and practicable, exhibiting remarkable substrate generality.
{"title":"PIDA‐Enabled C3‐Amination of Imidazopyridines with Primary Aromatic Amines Using Rongalite as In Situ C1 Source","authors":"Hui‐Ying Ren , Miao Wang , Shan Jiang , Yang‐Yang Zhou , Zi‐Xiang Lu , Cheng Xu , Bang‐Tun Zhao","doi":"10.1002/ajoc.70189","DOIUrl":"10.1002/ajoc.70189","url":null,"abstract":"<div><div>Imidazo[1,2‐a]pyridine represents a significant heterocyclic scaffold, and its C3‐aminated derivatives demonstrate enhanced bioactivity. However, employing primary arylamines directly as aminating agents remains challenging to date. Herein, we report the PIDA‐enabled C3‐amination of imidazopyridines employing primary aromatic amines as the amination reagents, with rongalite as an in situ C1‐building block. This approach addresses the substrate scope limitations in C3‐amination reactions of imidazopyridines using primary aromatic amines. Mechanistic investigations have demonstrated that rongalite serves as a reactive C1 synthon, initially enabling C3‐aminomethylation of imidazopyridines with primary aromatic amines, followed by PIDA‐enabled 1,2‐<em>ipso</em>‐migration to achieve C3‐amination. This C3‐amination protocol is highly efficient and practicable, exhibiting remarkable substrate generality.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70189"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500843","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}
The first example of a novel fluoranthene‐embedded doubly fused expanded porphyrin was synthesized by [3 + 2] condensation of newly synthesized fluoranthene‐based tripyrrane with readily available bithiophene diol in CH2Cl2 under mild acid‐catalyzed inert atmosphere conditions at room temperature, followed by DDQ oxidation in open air. 1D and 2D NMR spectroscopy and MALDI‐TOF analysis indicated that the two thiophene rings of the bithiophene moiety were inverted and the inner C's of the two inverted thiophene rings were involved in bond formation with adjacent pyrrole N's to generate two fused tripentacyclic rings as a part of macrocyclic framework. DFT optimized structure revealed that the macrocycle was highly contorted and adopted saddle‐like structure and the fluoranthene unit in the macrocycle was deviated by an angle of 58.34° with respect to the “mean plane” defined by four meso‐carbons. The macrocycle showed broad and ill‐defined absorption bands in the 300–750 nm region and electrochemical studies revealed that the macrocycle was easier to oxidize, indicating the electron‐rich nature of the fluoranthene embedded doubly fused expanded porphyrin. DFT/TD‐DFT studies were in agreement with the experimental observations.
{"title":"Fluoranthene Embedded Doubly Fused Expanded Porphyrin","authors":"Vratta Grover , Prof. Dr. Mangalampalli Ravikanth","doi":"10.1002/ajoc.70181","DOIUrl":"10.1002/ajoc.70181","url":null,"abstract":"<div><div>The first example of a novel fluoranthene‐embedded doubly fused expanded porphyrin was synthesized by [3 + 2] condensation of newly synthesized fluoranthene‐based tripyrrane with readily available bithiophene diol in CH<sub>2</sub>Cl<sub>2</sub> under mild acid‐catalyzed inert atmosphere conditions at room temperature, followed by DDQ oxidation in open air. 1D and 2D NMR spectroscopy and MALDI‐TOF analysis indicated that the two thiophene rings of the bithiophene moiety were inverted and the inner C's of the two inverted thiophene rings were involved in bond formation with adjacent pyrrole N's to generate two fused tripentacyclic rings as a part of macrocyclic framework. DFT optimized structure revealed that the macrocycle was highly contorted and adopted saddle‐like structure and the fluoranthene unit in the macrocycle was deviated by an angle of 58.34° with respect to the “mean plane” defined by four <em>meso‐</em>carbons. The macrocycle showed broad and ill‐defined absorption bands in the 300–750 nm region and electrochemical studies revealed that the macrocycle was easier to oxidize, indicating the electron‐rich nature of the fluoranthene embedded doubly fused expanded porphyrin. DFT/TD‐DFT studies were in agreement with the experimental observations.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70181"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500958","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}
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