Sineenart Attanonchai , Kasam Poonswat , Prof. Dr. Somsak Ruchirawat , Dr. Poonsakdi Ploypradith
The cascade carbocation cyclization (CCC) of the secondary benzylic, or the benzhydryl, carbocation by the 2‐indene, 2/3‐indole, or 2/3‐benzofuran followed by the intermolecular nucleophilic addition by H‐/allyl‐silane or electron‐rich arenes, also classifiable as the interrupted iso‐Nazarov reaction, provided the corresponding indane‐fused indane/indole/benzofuran scaffolds. The initial CCC forged the trans relationship at the two newly formed adjacent stereogenic centers while the latter provided the selective cis stereocontrol at the new ring junction. Starting from achiral alcohols, the reaction sequence furnished the oxygen/nitrogen‐containing indane fused‐ring tetracyclic systems in moderate to good yields with excellent stereoselectivity on all three contiguous chiral centers.
{"title":"Indenoindenes, Indenoindoles, and Indenobenzofurans via the Interrupted iso‐Nazarov Reaction","authors":"Sineenart Attanonchai , Kasam Poonswat , Prof. Dr. Somsak Ruchirawat , Dr. Poonsakdi Ploypradith","doi":"10.1002/ajoc.202400655","DOIUrl":"10.1002/ajoc.202400655","url":null,"abstract":"<div><div>The cascade carbocation cyclization (CCC) of the secondary benzylic, or the benzhydryl, carbocation by the 2‐indene, 2/3‐indole, or 2/3‐benzofuran followed by the intermolecular nucleophilic addition by H‐/allyl‐silane or electron‐rich arenes, also classifiable as the interrupted <em>iso</em>‐Nazarov reaction, provided the corresponding indane‐fused indane/indole/benzofuran scaffolds. The initial CCC forged the <em>trans</em> relationship at the two newly formed adjacent stereogenic centers while the latter provided the selective <em>cis</em> stereocontrol at the new ring junction. Starting from achiral alcohols, the reaction sequence furnished the oxygen/nitrogen‐containing indane fused‐ring tetracyclic systems in moderate to good yields with excellent stereoselectivity on all three contiguous chiral centers.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400655"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622343","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}
Ruijun Jiang , Tingting Qin , Yiping Wang , Huicong Cui , Yanping Shi , Lei Zhang , Dr. Xuguang Liu
Ullazine, a typical polycyclic aromatic hydrocarbon with a 14 π‐electron nitrogen‐containing core, has garnered significant attention due to its excellent performance in optoelectronics applications. Integration of heteroatoms into the frameworks of polycyclic aromatic hydrocarbons is a well‐established strategy for modifying molecular characteristics and functionalities. In this study, heteroatom‐doped ullazine congener Bis‐BS‐U containing two boron‐sulfur bonds was synthesized. The structures and properties of Bis‐BS‐U were systematically compared to those of the previously reported bis‐boron/nitrogen doped ullazine (Bis‐BN‐U) and bis‐boron/oxygen doped ullazine (Bis‐BO‐U). Notably, the absorption and fluorescence spectra of Bis‐BS‐U exhibited a pronounced red shift relative to those of Bis‐BN‐U and Bis‐BO‐U. Theoretical calculations suggest that the boron/sulfur six‐member ring in Bis‐BS‐U exhibits very weak antiaromaticity. Moreover, the fluorescence intensity of Bis‐BS‐U showed an initial increase upon addition of Hg2+, followed by gradual decrease over time. This study expands the family of ullazine and provides valuable insights for the future development of heteroatom‐doped ullazines.
{"title":"Synthesis of a Bis‐Boron/Sulfur Doped Ullazine and Direct Comparison with Its Boron/Nitrogen and Boron/Oxygen Analogues","authors":"Ruijun Jiang , Tingting Qin , Yiping Wang , Huicong Cui , Yanping Shi , Lei Zhang , Dr. Xuguang Liu","doi":"10.1002/ajoc.202400637","DOIUrl":"10.1002/ajoc.202400637","url":null,"abstract":"<div><div>Ullazine, a typical polycyclic aromatic hydrocarbon with a 14 π‐electron nitrogen‐containing core, has garnered significant attention due to its excellent performance in optoelectronics applications. Integration of heteroatoms into the frameworks of polycyclic aromatic hydrocarbons is a well‐established strategy for modifying molecular characteristics and functionalities. In this study, heteroatom‐doped ullazine congener <strong>Bis‐BS‐U</strong> containing two boron‐sulfur bonds was synthesized. The structures and properties of <strong>Bis‐BS‐U</strong> were systematically compared to those of the previously reported bis‐boron/nitrogen doped ullazine (<strong>Bis‐BN‐U</strong>) and bis‐boron/oxygen doped ullazine (<strong>Bis‐BO‐U</strong>). Notably, the absorption and fluorescence spectra of <strong>Bis‐BS‐U</strong> exhibited a pronounced red shift relative to those of <strong>Bis‐BN‐U</strong> and <strong>Bis‐BO‐U</strong>. Theoretical calculations suggest that the boron/sulfur six‐member ring in <strong>Bis‐BS‐U</strong> exhibits very weak antiaromaticity. Moreover, the fluorescence intensity of <strong>Bis‐BS‐U</strong> showed an initial increase upon addition of Hg<sup>2+</sup>, followed by gradual decrease over time. This study expands the family of ullazine and provides valuable insights for the future development of heteroatom‐doped ullazines.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400637"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622449","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}
We demonstrated that indium bromide, a trivalent indium compound with strong tolerance toward various coordination functional groups, can be used as a sole promotor to effectively promote the hydrohydrazination of a variety of N‐phenylhydrazines with aromatic/aliphatic alkynes and the subsequent [3,3]‐sigmatropic reaction of the hydrazone intermediate, leading to the one‐pot preparation of various poly‐substituted indole derivatives. Notably, the initial hydrohydrazination proceeded in a Markovnikov‐type manner and showed high regioselectivity, with the hydrohydrazination of arylalkynes affording only 2‐arylindole derivatives. Therefore, our findings provide a facile and practical one‐pot process for the synthesis of polysubstituted indole derivatives from various phenylhydrazines and aromatic/aliphatic alkynes using only one promotor.
{"title":"One‐Pot Synthesis of Polysubstituted Indoles via the Indium‐Promoted Regioselective Hydrohydrazination of Terminal Alkynes","authors":"Norio Sakai , Takahiro Yokoyama , Kento Ishida","doi":"10.1002/ajoc.202400682","DOIUrl":"10.1002/ajoc.202400682","url":null,"abstract":"<div><div>We demonstrated that indium bromide, a trivalent indium compound with strong tolerance toward various coordination functional groups, can be used as a sole promotor to effectively promote the hydrohydrazination of a variety of <em>N</em>‐phenylhydrazines with aromatic/aliphatic alkynes and the subsequent [3,3]‐sigmatropic reaction of the hydrazone intermediate, leading to the one‐pot preparation of various poly‐substituted indole derivatives. Notably, the initial hydrohydrazination proceeded in a Markovnikov‐type manner and showed high regioselectivity, with the hydrohydrazination of arylalkynes affording only 2‐arylindole derivatives. Therefore, our findings provide a facile and practical one‐pot process for the synthesis of polysubstituted indole derivatives from various phenylhydrazines and aromatic/aliphatic alkynes using only one promotor.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400682"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400682","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622637","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}
Dr. Archana Velloth , Piyush Kumar , Shabana Butt , Dr. Sugumar Venkataramani
C–Centered radicals are one of the classical reactive intermediates that have shown enormous utility in organic synthesis. Besides homolytic bond cleavages, the advancements of electron transfer‐based photoredox and electroredox processes are popular choices for their generation and synthetic explorations. Considering the widespread attention and versatility of C‐centered radicals in several fields, a systematic understanding of structural, stability, and reactivity aspects is crucial for the further development and futuristic applications of radical chemistry. In this regard, several topics pertaining to the generation, detection, and studies relevant to radical chemistry in general and thermodynamic and kinetic stability of the C‐centered radicals specifically, with a major emphasis on physical organic chemistry aspects, are presented. Besides portraying the factors governing their stability and reactivity, this contribution also discusses their challenges and perspectives.
{"title":"C–Centered Radicals: Generation, Detection, Stability and Perspectives","authors":"Dr. Archana Velloth , Piyush Kumar , Shabana Butt , Dr. Sugumar Venkataramani","doi":"10.1002/ajoc.202400686","DOIUrl":"10.1002/ajoc.202400686","url":null,"abstract":"<div><div><em>C–</em>Centered radicals are one of the classical reactive intermediates that have shown enormous utility in organic synthesis. Besides homolytic bond cleavages, the advancements of electron transfer‐based photoredox and electroredox processes are popular choices for their generation and synthetic explorations. Considering the widespread attention and versatility of <em>C</em>‐centered radicals in several fields, a systematic understanding of structural, stability, and reactivity aspects is crucial for the further development and futuristic applications of radical chemistry. In this regard, several topics pertaining to the generation, detection, and studies relevant to radical chemistry in general and thermodynamic and kinetic stability of the <em>C</em>‐centered radicals specifically, with a major emphasis on physical organic chemistry aspects, are presented. Besides portraying the factors governing their stability and reactivity, this contribution also discusses their challenges and perspectives.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400686"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622727","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. Toreshettahally R. Swaroop , Dr. Rajaghatta N. Suresh , Dr. Muddegowda Umashankara , Dr. Kanchugarakoppal S. Rangappa
In this review, we have discussed the various types of organic electrochemical reactions which use catalytic/sub‐stoichiometric amount of inorganic and/or organic salts as electrolytes. We have also presented the plausible mechanism of each electro‐organic reaction. This review article highlights notable examples of electro‐organic synthesis published from 2000 to 2023.
{"title":"A Review on Use of Electrolytes in Catalytic/ Sub‐Stoichiometric Amounts in Electro‐Organic Synthesis: A Much Greener Approach","authors":"Dr. Toreshettahally R. Swaroop , Dr. Rajaghatta N. Suresh , Dr. Muddegowda Umashankara , Dr. Kanchugarakoppal S. Rangappa","doi":"10.1002/ajoc.202400307","DOIUrl":"10.1002/ajoc.202400307","url":null,"abstract":"<div><div>In this review, we have discussed the various types of organic electrochemical reactions which use catalytic/sub‐stoichiometric amount of inorganic and/or organic salts as electrolytes. We have also presented the plausible mechanism of each electro‐organic reaction. This review article highlights notable examples of electro‐organic synthesis published from 2000 to 2023.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400307"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622705","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. Isao Mizota , Keiji Oshima , Nozomi Hoshiai , Ayaki Yamamoto , Masaki Mitani , Rabbia Batool , Prof. Dr. Bo‐Tau Liu , Prof. Dr. Makoto Shimizu
2H‐1,4‐Oxazin‐3(4H)‐One Derivatives Are Known to Exhibit a Wide Range of Biological Activities Such as Antifungal, Anticancer, as Receptor Antagonists and Potassium Channel Modulators. In This Report, We Describe That α‐Hydrazonoketone Is an Appropriate Substrate for the Umpolung Reaction and a Promising Candidate for the Synthesis of 2H‐1,4‐Oxazine‐3(4H)‐Ones. Notably, Umpolung N‐Methylation for α‐Hydrazonoketone Proceeded Quantitatively in a Mild and Extremely Short Reaction Time, Which Has Been Difficult to Achieve in the Conventional Reactions. Moreover, We Also Developed Tandem Umpolung Reaction/Reduction/N‐Acyl‐O‐Alkylation to Afford 2H‐1,4‐Oxazin‐3(4H)‐Ones in High Yield in the Presence of Chloroacetyl Chloride.
{"title":"Synthesis of 2H‐1,4‐Oxazin‐3(4H)‐One Utilizing Umpolung Reaction to α‐Hydrazonoketone","authors":"Dr. Isao Mizota , Keiji Oshima , Nozomi Hoshiai , Ayaki Yamamoto , Masaki Mitani , Rabbia Batool , Prof. Dr. Bo‐Tau Liu , Prof. Dr. Makoto Shimizu","doi":"10.1002/ajoc.202400698","DOIUrl":"10.1002/ajoc.202400698","url":null,"abstract":"<div><div>2<em>H</em>‐1,4‐Oxazin‐3(4<em>H</em>)‐One Derivatives Are Known to Exhibit a Wide Range of Biological Activities Such as Antifungal, Anticancer, as Receptor Antagonists and Potassium Channel Modulators. In This Report, We Describe That α‐Hydrazonoketone Is an Appropriate Substrate for the Umpolung Reaction and a Promising Candidate for the Synthesis of 2<em>H</em>‐1,4‐Oxazine‐3(4<em>H</em>)‐Ones. Notably, Umpolung <em>N</em>‐Methylation for α‐Hydrazonoketone Proceeded Quantitatively in a Mild and Extremely Short Reaction Time, Which Has Been Difficult to Achieve in the Conventional Reactions. Moreover, We Also Developed Tandem Umpolung Reaction/Reduction/<em>N‐</em>Acyl<em>‐O</em>‐Alkylation to Afford 2<em>H</em>‐1,4‐Oxazin‐3(4<em>H</em>)‐Ones in High Yield in the Presence of Chloroacetyl Chloride.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400698"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400698","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622286","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}
Dr. Alexander Yu. Simonov , Dr. Alexey A. Panov , Dr. Andrei V. Churakov , Prof. Dr. Vladimir I. Polshakov , Prof. Dr. Igor B. Levshin
The reaction of thiazolidine‐2,4‐diones (TZDs) with oxiranes has been thoroughly investigated. For the first time, it has been observed that 5‐arylidene‐TZD derivatives can undergo transformation into 6‐substituted 1,4‐oxathian‐2‐ones. Additionally, it has been demonstrated that certain 3‐substituted 5‐arylidene‐TZDs can convert to 1,4‐oxathian‐2‐ones and oxazolidines upon reaction with oxiranes, confirming that the process follows a cascade mechanism. Several factors have been found to influence the reaction‘s outcome, including the amount of oxirane, the presence of a base, and solvent polarity. It has been determined that dimethylformamide (DMF) is essential for the reaction to proceed efficiently. Furthermore, the critical role of the benzylidene group in facilitating the reaction has been confirmed. An unusual hydrogen bond between the ortho‐hydrogens of the phenyl group and the sulfur atom of the thiazolidine ring, observed via NMR spectroscopy, highlights the sulfur atom‘s strong electron‐accepting properties, which play a key role in the observed transformations.
{"title":"Oxirane‐Driven Cascade Transformations of 5‐Arylidene‐Thiazolidine‐2,4‐Diones","authors":"Dr. Alexander Yu. Simonov , Dr. Alexey A. Panov , Dr. Andrei V. Churakov , Prof. Dr. Vladimir I. Polshakov , Prof. Dr. Igor B. Levshin","doi":"10.1002/ajoc.202400645","DOIUrl":"10.1002/ajoc.202400645","url":null,"abstract":"<div><div>The reaction of thiazolidine‐2,4‐diones (TZDs) with oxiranes has been thoroughly investigated. For the first time, it has been observed that 5‐arylidene‐TZD derivatives can undergo transformation into 6‐substituted 1,4‐oxathian‐2‐ones. Additionally, it has been demonstrated that certain 3‐substituted 5‐arylidene‐TZDs can convert to 1,4‐oxathian‐2‐ones and oxazolidines upon reaction with oxiranes, confirming that the process follows a cascade mechanism. Several factors have been found to influence the reaction‘s outcome, including the amount of oxirane, the presence of a base, and solvent polarity. It has been determined that dimethylformamide (DMF) is essential for the reaction to proceed efficiently. Furthermore, the critical role of the benzylidene group in facilitating the reaction has been confirmed. An unusual hydrogen bond between the ortho‐hydrogens of the phenyl group and the sulfur atom of the thiazolidine ring, observed via NMR spectroscopy, highlights the sulfur atom‘s strong electron‐accepting properties, which play a key role in the observed transformations.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400645"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622349","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}
Yang Sun , Yiyan Wang , Lijun Zhang , Rui Zhong , Hui Wang
A rhodium‐catalyzed cascade C−H allylation combined with exo‐ and endo‐type [3+2] dipolar cycloaddition of aryl azomethine imines with Morita‐Baylis‐Hillman (MBH) adducts and allyl acetates is described. This process, which is operationally simple and proceeds efficiently in air and moisture under neat conditions, facilitates diverse bridged and fused tetracycles as single diastereomers. The reaction showcases a broad substrate scope and good functional group compatibility. Furthermore, its practicality is further demonstrated through successful scale‐up and synthetic applications.
{"title":"Synthesis of Bridged and Fused Tetracycles via Rhodium‐Catalyzed C−H Allylation/Cycloaddition of Azomethine Imines with MBH Adducts and Allyl Acetates","authors":"Yang Sun , Yiyan Wang , Lijun Zhang , Rui Zhong , Hui Wang","doi":"10.1002/ajoc.202400646","DOIUrl":"10.1002/ajoc.202400646","url":null,"abstract":"<div><div>A rhodium‐catalyzed cascade C−H allylation combined with <em>exo</em>‐ and <em>endo</em>‐type [3+2] dipolar cycloaddition of aryl azomethine imines with Morita‐Baylis‐Hillman (MBH) adducts and allyl acetates is described. This process, which is operationally simple and proceeds efficiently in air and moisture under neat conditions, facilitates diverse bridged and fused tetracycles as single diastereomers. The reaction showcases a broad substrate scope and good functional group compatibility. Furthermore, its practicality is further demonstrated through successful scale‐up and synthetic applications.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400646"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622355","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 fluorescent pyridinium‐based chemosensor (E)‐1‐(2‐(3‐hydroxy‐4‐((pyridin‐2‐ylimino) methyl) phenoxy) ethyl) pyridin‐1‐ium bromide (BzPySB) was synthesized and characterized using various spectroscopic techniques. The chemosensing potential of BzPySB was explored using UV‐vis and fluorescence spectroscopy in the aqueous medium. The turn‐on fluorescence behavior was observed for BzPySB in the presence of Al3+, while other metal ions were non‐responsive. The B−H and Job′s plot confirmed the 1 : 1 stoichiometric ratio of the BzPySB and Al3+. The in situ generated complex BzPySB‐Al3+ offered selectivity toward TNP via fluorescence turn‐off phenomena with high Ksv and LOD values. The “off‐on‐off” sensing mechanism was elucidated through 1H NMR, mass spectrometry, and DFT calculations. The probe also detected Al3+ in plant and MCF‐7 cells, highlighting its potential in biological systems. Moreover, BzPySB exhibited solid‐state luminescent properties credited to weak π‐π interaction, leading to its successful application in the visualization of latent fingerprints.
{"title":"Pyridinium‐Based Schiff‐Base Fluorescent Chemosensor for Sequential Detection of Al3+ Ions and TNP: Applications in Cell Imaging and Latent Fingerprint Visualization","authors":"Pragya , Sonali J. Jain , Krishnan Rangan , Prabhat Nath Jha , Bharti Khungar","doi":"10.1002/ajoc.202400669","DOIUrl":"10.1002/ajoc.202400669","url":null,"abstract":"<div><div>A fluorescent pyridinium‐based chemosensor (E)‐1‐(2‐(3‐hydroxy‐4‐((pyridin‐2‐ylimino) methyl) phenoxy) ethyl) pyridin‐1‐ium bromide (<strong>BzPySB</strong>) was synthesized and characterized using various spectroscopic techniques. The chemosensing potential of <strong>BzPySB</strong> was explored using UV‐vis and fluorescence spectroscopy in the aqueous medium. The turn‐on fluorescence behavior was observed for <strong>BzPySB</strong> in the presence of Al<sup>3+</sup>, while other metal ions were non‐responsive. The B−H and Job′s plot confirmed the 1 : 1 stoichiometric ratio of the <strong>BzPySB</strong> and Al<sup>3+</sup>. The in situ generated complex <strong>BzPySB</strong>‐Al<sup>3+</sup> offered selectivity toward TNP via fluorescence turn‐off phenomena with high <em>K</em><sub>sv</sub> and LOD values. The “off‐on‐off” sensing mechanism was elucidated through <sup>1</sup>H NMR, mass spectrometry, and DFT calculations. The probe also detected Al<sup>3+</sup> in plant and MCF‐7 cells, highlighting its potential in biological systems. Moreover, <strong>BzPySB</strong> exhibited solid‐state luminescent properties credited to weak <em>π‐π</em> interaction, leading to its successful application in the visualization of latent fingerprints.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400669"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622492","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}
Juan Tian , Shimin Yang , Ying Peng , Mengyun Chen , Xin Chen , Xinyi Wang , Dayong Sang
N‐Acylsulfonamides play a significant role in organic and medicinal chemistry. The N‐deacylation of N‐acylsulfonamides is an important transformation that releases the sulfonamide structural motif. Herein, a metal triflimide‐catalyzed nonhydrolytic method for the deacylation of N‐acylsulfonamides is presented. Commercially available metal triflimides reactive for the N‐deacylation include Cu(NTf2)2, Zn(NTf2)2, Mg(NTf2)2, Ce(NTf2)3, and La(NTf2)3. A range of N‐acyl groups, including acetyl, propionyl, butyryl, isobutyryl, octanoyl, benzoyl, 2‐phenylacetyl, and sterically hindered pivaloyl are readily deblocked efficiently. A variety of functional groups, such as halogeno, keto, nitro, cyano, ether, and carboxylate, are tolerated intact.
{"title":"Deacylation of N‐Acylsulfonamides Mediated by Metal Triflimides","authors":"Juan Tian , Shimin Yang , Ying Peng , Mengyun Chen , Xin Chen , Xinyi Wang , Dayong Sang","doi":"10.1002/ajoc.202400673","DOIUrl":"10.1002/ajoc.202400673","url":null,"abstract":"<div><div><em>N</em>‐Acylsulfonamides play a significant role in organic and medicinal chemistry. The <em>N</em>‐deacylation of <em>N</em>‐acylsulfonamides is an important transformation that releases the sulfonamide structural motif. Herein, a metal triflimide‐catalyzed nonhydrolytic method for the deacylation of <em>N</em>‐acylsulfonamides is presented. Commercially available metal triflimides reactive for the <em>N</em>‐deacylation include Cu(NTf<sub>2</sub>)<sub>2</sub>, Zn(NTf<sub>2</sub>)<sub>2</sub>, Mg(NTf<sub>2</sub>)<sub>2</sub>, Ce(NTf<sub>2</sub>)<sub>3</sub>, and La(NTf<sub>2</sub>)<sub>3</sub>. A range of <em>N</em>‐acyl groups, including acetyl, propionyl, butyryl, isobutyryl, octanoyl, benzoyl, 2‐phenylacetyl, and sterically hindered pivaloyl are readily deblocked efficiently. A variety of functional groups, such as halogeno, keto, nitro, cyano, ether, and carboxylate, are tolerated intact.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400673"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622288","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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