Jitendra K. Chavan , Jagadeesh Babu Nanubolu , Haridas B. Rode
A selectfluor‐mediated metal‐free approach has been developed for the synthesis of methylene‐bound benzotriazolation, triazolation, and pyrazolation of 3‐acetylindoles at 90°C. The reaction is kinetically controlled and uses DMSO as one carbon source. Further, α‐methylenation of 3‐acetylindoles was observed when benzotriazole, triazole, and pyrazole were absent in the reaction at a higher temperature (120°C). The reaction uses DMSO as one‐carbon synthon and is thermodynamically controlled. The base is needed for α‐methylenation of 3‐acetylindoles. The current method expands the scope of metal‐free organic reactions and offers new opportunities for developing a library of bioactive indoles for pharmaceutical science.
{"title":"Selectfluor‐Mediated Synthesis of Methylene‐Bound Heteroamination and α‐Methylenation of 3‐Acetylindoles Using DMSO as a One‐Carbon Source","authors":"Jitendra K. Chavan , Jagadeesh Babu Nanubolu , Haridas B. Rode","doi":"10.1002/ajoc.70281","DOIUrl":"10.1002/ajoc.70281","url":null,"abstract":"<div><div>A selectfluor‐mediated metal‐free approach has been developed for the synthesis of methylene‐bound benzotriazolation, triazolation, and pyrazolation of 3‐acetylindoles at 90°C. The reaction is kinetically controlled and uses DMSO as one carbon source. Further, <em>α</em>‐methylenation of 3‐acetylindoles was observed when benzotriazole, triazole, and pyrazole were absent in the reaction at a higher temperature (120°C). The reaction uses DMSO as one‐carbon synthon and is thermodynamically controlled. The base is needed for <em>α</em>‐methylenation of 3‐acetylindoles. The current method expands the scope of metal‐free organic reactions and offers new opportunities for developing a library of bioactive indoles for pharmaceutical science.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70281"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145891354","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}
Aryl benzene sulfonyl hydrazide derivatives containing electron‐donor and electron‐acceptor groups were successfully synthesized and reported via a one‐pot manner, which showed remarkable optical properties. The changes in fluorescence properties of compound 5a in the presence of various cations were evaluated. Compound 5a can act as a fluorescence sensor for susceptible and selective detection of As3+ and Ru3+ in DMSO. DFT calculation was done to elucidate the mechanisms. Selectively respond to detecting As3+ and Ru3+ with enhanced and quenched fluorescence, respectively. The fluorescence of Job's plot supported the fluorescence of 5a, As3+, and Ru3+, as well as the sensing mechanism of the 1:1 binding system. The binding constants for the 5a + As3+ and 5a + Ru3+ were found to be 4.83 × 10−5 M−1 and 1.91 × 10−5 M−1, with LOD attained 1.91 × 10−7 M−1 for As3+, and 2.01 × 10−7 M−1 for Ru3+, respectively.
{"title":"One‐Pot Synthesis of Aryl Benzene Sulfonyl Hydrazides for Fluorescent Chemo Sensing of As3+ and Ru3+","authors":"Murugesan Preethi , Rameshbabu Ajaydev , Sivakumar Shanmugam","doi":"10.1002/ajoc.70275","DOIUrl":"10.1002/ajoc.70275","url":null,"abstract":"<div><div>Aryl benzene sulfonyl hydrazide derivatives containing electron‐donor and electron‐acceptor groups were successfully synthesized and reported <em>via</em> a one‐pot manner, which showed remarkable optical properties. The changes in fluorescence properties of compound <strong>5a</strong> in the presence of various cations were evaluated. Compound <strong>5a</strong> can act as a fluorescence sensor for susceptible and selective detection of As<sup>3+</sup> and Ru<sup>3+</sup> in DMSO. DFT calculation was done to elucidate the mechanisms. Selectively respond to detecting As<sup>3+</sup> and Ru<sup>3+</sup> with enhanced and quenched fluorescence, respectively. The fluorescence of Job's plot supported the fluorescence of <strong>5a,</strong> As<sup>3+</sup>, and Ru<sup>3+</sup>, as well as the sensing mechanism of the 1:1 binding system. The binding constants for the 5a + As<sup>3+</sup> and 5a + Ru<sup>3+</sup> were found to be 4.83 × 10<sup>−5 </sup>M<sup>−1</sup> and 1.91 × 10<sup>−5</sup> M<sup>−1</sup>, with LOD attained 1.91 × 10<sup>−7</sup> M<sup>−1</sup> for As<sup>3+</sup>, and 2.01 × 10<sup>−7</sup> M<sup>−1</sup> for Ru<sup>3+</sup>, respectively.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70275"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145891468","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}
Xiangyun Zheng , Yingying Xu , Xiangtu Tu , Xuebin Zhang , Quan Zhou , Haiwei Ye , Yang Song , Chen Xu , Shuyu Xie
An additive‐free and metal‐free three‐component radical relay reaction has been achieved to obtain diverse sulfonylated polycyclic indolines with moderate to excellent yields. This innovative protocol offers several significant advantages: (1) it eliminates the need for transition metal catalysts, (2) operates under mild reaction conditions without requiring high temperatures, and (3) demonstrates exceptional diastereoselectivity (dr > 20:1). Comprehensive mechanistic studies have revealed that the transformation proceeds through an intramolecular 1,5‐hydrogen atom transfer (1,5‐HAT) process.
{"title":"Diastereoselective Three‐Component Annulation for the Synthesis of Sulfonylated Polycyclic Indolines","authors":"Xiangyun Zheng , Yingying Xu , Xiangtu Tu , Xuebin Zhang , Quan Zhou , Haiwei Ye , Yang Song , Chen Xu , Shuyu Xie","doi":"10.1002/ajoc.70284","DOIUrl":"10.1002/ajoc.70284","url":null,"abstract":"<div><div>An additive‐free and metal‐free three‐component radical relay reaction has been achieved to obtain diverse sulfonylated polycyclic indolines with moderate to excellent yields. This innovative protocol offers several significant advantages: (1) it eliminates the need for transition metal catalysts, (2) operates under mild reaction conditions without requiring high temperatures, and (3) demonstrates exceptional diastereoselectivity (dr > 20:1). Comprehensive mechanistic studies have revealed that the transformation proceeds through an intramolecular 1,5‐hydrogen atom transfer (1,5‐HAT) process.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70284"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887481","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}
Huan‐Zhu Xue , Zhi‐Kui Cao , Mei‐Ting Zhao , Kai‐Cheng Yang , Long Chen
We herein reported a formal [3+3] cyclization reaction between 3‐alkynyl‐3‐hydroxyisoindolinones and substituted phenols, which offered an efficient procedure for the preparation of 2H‐chromene‐based spiro‐isoindolinones. 10 mol% of inexpensive catalyst (Cu(ClO4)2·6H2O or Fe(OTf)3) proved to be the best to promote the tandem regioselective 1,4‐addition of phenols to the in situ generated β,γ‐alkynyl‐α‐ketimine/intramolecular O‐Michael addition to afford the desired products under mild conditions (25°C, 0.5–24 h) with a broad substrate scope (31 examples) in up to 99% yield. The synthetic utility was demonstrated by the scaled synthesis and further elaboration of the obtained products to polycyclic compounds bearing isoindolinone, 2H‐chromene and five or six‐membered O‐heterocycles.
{"title":"Formal [3+3] Cyclization Between 3‐Alkynyl‐3‐hydroxyisoindolinones and Substituted Phenols to 2H‐Chromene Based Spiro‐isoindolinones","authors":"Huan‐Zhu Xue , Zhi‐Kui Cao , Mei‐Ting Zhao , Kai‐Cheng Yang , Long Chen","doi":"10.1002/ajoc.70260","DOIUrl":"10.1002/ajoc.70260","url":null,"abstract":"<div><div>We herein reported a formal [3+3] cyclization reaction between 3‐alkynyl‐3‐hydroxyisoindolinones and substituted phenols, which offered an efficient procedure for the preparation of 2<em>H</em>‐chromene‐based <em>spiro</em>‐isoindolinones. 10 mol% of inexpensive catalyst (Cu(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O or Fe(OTf)<sub>3</sub>) proved to be the best to promote the tandem regioselective 1,4‐addition of phenols to the in situ generated <em>β</em>,<em>γ</em>‐alkynyl‐<em>α</em>‐ketimine/intramolecular <em>O</em>‐Michael addition to afford the desired products under mild conditions (25°C, 0.5–24 h) with a broad substrate scope (31 examples) in up to 99% yield. The synthetic utility was demonstrated by the scaled synthesis and further elaboration of the obtained products to polycyclic compounds bearing isoindolinone, 2<em>H</em>‐chromene and five or six‐membered <em>O</em>‐heterocycles.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70260"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887280","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}
Sara Mohammed Bedaiwi , Karnan Manickavasakam , Yuda Prima Hardianto , Abdulmajid A. Mirghni , Syed Shaheen Shah , M. Nasiruzzaman Shaikh , Mohammad Rezaul Karim , Basil Osama Ahmed , Md. Abdul Aziz
The growing demand for flexible, sustainable, and multifunctional energy storage systems has spurred interest in low‐cost, biomass‐derived materials for next‐generation supercapacitors (SCs). This study presents a sustainable organic route to fabricate activated carbon (AC) from jute sticks and a fluoropolymer membrane based on PVDF‐HFP, targeting dual applications in piezoelectric and aqueous asymmetric SC configurations. In the self‐charging system, jute‐derived AC is employed as both electrodes, while the PVDF‐HFP membrane functions simultaneously as a separator and a piezoelectric energy harvester. For the asymmetric configuration, the AC serves as the negative electrode, paired with a Ni‐based metal–organic framework (Ni‐MOF) as the positive electrode, demonstrating the versatility of the biomass‐derived carbon in hybrid energy storage systems. The piezoelectric SC achieves an areal capacitance of 72 mF/cm2 and effectively converts mechanical energy into electrical energy under applied pressure. Meanwhile, the asymmetric device delivers an areal capacitance of 117 mF/cm2, showcasing enhanced charge storage and energy delivery. This dual‐application approach highlights the multifunctional potential of jute‐derived carbon and fluoropolymer membranes, offering a scalable and environment‐friendly pathway for the development of autonomous, self‐powered, and portable electronic systems.
{"title":"Sustainable Organic Routes to Activated Carbon and Fluoropolymer Membranes for Supercapacitor Applications","authors":"Sara Mohammed Bedaiwi , Karnan Manickavasakam , Yuda Prima Hardianto , Abdulmajid A. Mirghni , Syed Shaheen Shah , M. Nasiruzzaman Shaikh , Mohammad Rezaul Karim , Basil Osama Ahmed , Md. Abdul Aziz","doi":"10.1002/ajoc.70277","DOIUrl":"10.1002/ajoc.70277","url":null,"abstract":"<div><div>The growing demand for flexible, sustainable, and multifunctional energy storage systems has spurred interest in low‐cost, biomass‐derived materials for next‐generation supercapacitors (SCs). This study presents a sustainable organic route to fabricate activated carbon (AC) from jute sticks and a fluoropolymer membrane based on PVDF‐HFP, targeting dual applications in piezoelectric and aqueous asymmetric SC configurations. In the self‐charging system, jute‐derived AC is employed as both electrodes, while the PVDF‐HFP membrane functions simultaneously as a separator and a piezoelectric energy harvester. For the asymmetric configuration, the AC serves as the negative electrode, paired with a Ni‐based metal–organic framework (Ni‐MOF) as the positive electrode, demonstrating the versatility of the biomass‐derived carbon in hybrid energy storage systems. The piezoelectric SC achieves an areal capacitance of 72 mF/cm<sup>2</sup> and effectively converts mechanical energy into electrical energy under applied pressure. Meanwhile, the asymmetric device delivers an areal capacitance of 117 mF/cm<sup>2</sup>, showcasing enhanced charge storage and energy delivery. This dual‐application approach highlights the multifunctional potential of jute‐derived carbon and fluoropolymer membranes, offering a scalable and environment‐friendly pathway for the development of autonomous, self‐powered, and portable electronic systems.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70277"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887480","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}
Luying Song , Liming Wang , Renbo An , Wei Zhang , Ying Jin
Efficient stereoselective synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐diones through one‐pot condensation of an aldehyde, malononitrile (cyanoacetate) and phthalhydrazide is described for the first time. 1‐[3,5‐Bis(trifluoromethyl)phenyl]‐3‐[(1R,2R)‐2‐(pyrrolidin‐1‐yl)cyclohexyl]thiourea (Takemoto's catalyst) was identified as an optimal organocatalyst to promote the tandem Knoevenagel/Michael/cyclization reaction to yield the desired products in good yields (52%–92%) with up to 99% enantiomer excess (ee).
{"title":"Enantioselective Synthesis of 1H‐Pyrazolo[1,2‐b]pyridazine‐5,10‐dione Derivatives via an Organocatalytic Three‐Component Cascade Reaction","authors":"Luying Song , Liming Wang , Renbo An , Wei Zhang , Ying Jin","doi":"10.1002/ajoc.70245","DOIUrl":"10.1002/ajoc.70245","url":null,"abstract":"<div><div>Efficient stereoselective synthesis of 1<em>H</em>‐pyrazolo[1,2‐<em>b</em>]phthalazine‐5,10‐diones through one‐pot condensation of an aldehyde, malononitrile (cyanoacetate) and phthalhydrazide is described for the first time. 1‐[3,5‐Bis(trifluoromethyl)phenyl]‐3‐[(<em>1R,2R</em>)‐2‐(pyrrolidin‐1‐yl)cyclohexyl]thiourea (Takemoto's catalyst) was identified as an optimal organocatalyst to promote the tandem Knoevenagel/Michael/cyclization reaction to yield the desired products in good yields (52%–92%) with up to 99% enantiomer excess (ee).</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70245"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887303","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}
N‐hydroxyphthalimide (NHPI) has emerged as a versatile organocatalyst for the selective oxidation and functionalization of C(sp3)–H bonds via the phthalimide N‐oxyl (PINO) radical. In recent years, the NHPI–PINO platform has advanced significantly, driven by three key developments: photochemical activation, electrochemical transformation, and catalyst immobilization. Visible‐light‐driven systems and semiconductor‐assisted photocatalysis have expanded the reaction scope and enabled sustainable transformations under mild conditions. Electrochemical approaches have provided scalable and energy‐efficient routes for hydrogen atom transfer and radical functionalization, while cooperative electrocatalysis has further enhanced both activity and selectivity. Immobilizing NHPI on porous frameworks and hybrid supports has bridged the gap between homogeneous and heterogeneous catalysis, improving stability, recyclability, and compatibility with continuous‐flow systems. This review summarizes mechanistic insights and key breakthroughs from 2022 onward, highlighting the integration of advanced materials, operando spectroscopy, and computational modeling. Current challenges and future opportunities are also discussed, with a focus on hybrid catalytic platforms and the expansion of applications in synthetic, industrial, and sustainable chemistry.
n -羟基邻苯二胺（NHPI）是一种多用途的有机催化剂，可通过邻苯二胺n -氧基（PINO）自由基选择性氧化和功能化C(sp3) -H键。近年来，NHPI-PINO平台在光化学活化、电化学转化和催化剂固定化三个关键发展的推动下取得了显著进展。可见光驱动系统和半导体辅助光催化扩大了反应范围，并在温和条件下实现了可持续的转化。电化学方法为氢原子转移和自由基功能化提供了可扩展和节能的途径，而协同电催化进一步提高了活性和选择性。将NHPI固定在多孔框架和混合支架上，弥合了均相催化和多相催化之间的差距，提高了稳定性、可回收性以及与连续流系统的兼容性。本文总结了从2022年起的机理见解和关键突破，重点介绍了先进材料、operando光谱学和计算建模的集成。讨论了当前的挑战和未来的机遇，重点讨论了混合催化平台以及在合成、工业和可持续化学领域的应用扩展。
{"title":"Recent Advances in the NHPI–PINO Catalytic Cycle: Photochemical, Electrochemical, and Heterogenized NHPI/PINO Catalysis","authors":"Pijush Kanti Roy , Yutaka Hitomi","doi":"10.1002/ajoc.70293","DOIUrl":"10.1002/ajoc.70293","url":null,"abstract":"<div><div>N‐hydroxyphthalimide (NHPI) has emerged as a versatile organocatalyst for the selective oxidation and functionalization of C(sp<sup>3</sup>)–H bonds via the phthalimide N‐oxyl (PINO) radical. In recent years, the NHPI–PINO platform has advanced significantly, driven by three key developments: photochemical activation, electrochemical transformation, and catalyst immobilization. Visible‐light‐driven systems and semiconductor‐assisted photocatalysis have expanded the reaction scope and enabled sustainable transformations under mild conditions. Electrochemical approaches have provided scalable and energy‐efficient routes for hydrogen atom transfer and radical functionalization, while cooperative electrocatalysis has further enhanced both activity and selectivity. Immobilizing NHPI on porous frameworks and hybrid supports has bridged the gap between homogeneous and heterogeneous catalysis, improving stability, recyclability, and compatibility with continuous‐flow systems. This review summarizes mechanistic insights and key breakthroughs from 2022 onward, highlighting the integration of advanced materials, operando spectroscopy, and computational modeling. Current challenges and future opportunities are also discussed, with a focus on hybrid catalytic platforms and the expansion of applications in synthetic, industrial, and sustainable chemistry.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70293"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145983611","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}
Marjan Abedi , Ghodrat Mahmoudi , Atash V. Gurbanov , Raymond J. Butcher , Ömer Faruk Tutar , Elizaveta V. Panova , Damir A. Safin
An Isoniazid derivative, N'‐isonicotinoylnicotinohydrazonamide (1), was synthesized via a reaction between Isoniazid and 3‐cyanopyridine. It was established that 1 adopts a keto conformation in the solid state, forming a 2D supramolecular network stabilized by N─H⋯O and N─H⋯N hydrogen bonds. The NMR studies indicated the presence of two conformational isomers, a behavior attributed to the greater flexibility imparted by the meta‐positioned nitrogen in the nicotinoyl moiety, in contrast to its rigid picolinoyl‐containing isomer 2, which was reported by us previously. Hirshfeld surface analysis quantified the intermolecular interactions of 1, identifying H⋯H, H⋯C, H⋯N, and H⋯O contacts as the most significant contributors to the crystal packing. DFT calculations provided insights into the electronic structure, molecular electrostatic potential, and global reactivity descriptors, which characterized 1 as a strong electrophile. A combined QTAIM/NCI analysis confirmed the presence of prominent intramolecular interactions. In silico ADMET profiling of 1 predicted a favorable pharmacokinetic profile with high gastrointestinal absorption but potential hepatotoxicity and neurotoxicity. Molecular docking studies against key Mycobacterium tuberculosis proteins, viz. Proteasomal ATPase Mpa, Serine/threonine‐protein kinase, and Arabinosyltransferase, demonstrated that 1 exhibits superior binding affinity and ligand efficiency compared to the parent Isoniazid, suggesting its potential as a promising lead compound for anti‐tuberculosis drug development.
{"title":"N'‐Isonicotinoylnicotinohydrazonamide: Synthesis, Crystal Structure and Computational Studies","authors":"Marjan Abedi , Ghodrat Mahmoudi , Atash V. Gurbanov , Raymond J. Butcher , Ömer Faruk Tutar , Elizaveta V. Panova , Damir A. Safin","doi":"10.1002/ajoc.70292","DOIUrl":"10.1002/ajoc.70292","url":null,"abstract":"<div><div>An Isoniazid derivative, <em>N'</em>‐isonicotinoylnicotinohydrazonamide (<strong>1</strong>), was synthesized via a reaction between Isoniazid and 3‐cyanopyridine. It was established that <strong>1</strong> adopts a keto conformation in the solid state, forming a 2D supramolecular network stabilized by N─H⋯O and N─H⋯N hydrogen bonds. The NMR studies indicated the presence of two conformational isomers, a behavior attributed to the greater flexibility imparted by the <em>meta</em>‐positioned nitrogen in the nicotinoyl moiety, in contrast to its rigid picolinoyl‐containing isomer <strong>2</strong>, which was reported by us previously. Hirshfeld surface analysis quantified the intermolecular interactions of <strong>1</strong>, identifying H⋯H, H⋯C, H⋯N, and H⋯O contacts as the most significant contributors to the crystal packing. DFT calculations provided insights into the electronic structure, molecular electrostatic potential, and global reactivity descriptors, which characterized <strong>1</strong> as a strong electrophile. A combined QTAIM/NCI analysis confirmed the presence of prominent intramolecular interactions. In silico ADMET profiling of <strong>1</strong> predicted a favorable pharmacokinetic profile with high gastrointestinal absorption but potential hepatotoxicity and neurotoxicity. Molecular docking studies against key <em>Mycobacterium tuberculosis</em> proteins, viz. Proteasomal ATPase Mpa, Serine/threonine‐protein kinase, and Arabinosyltransferase, demonstrated that <strong>1</strong> exhibits superior binding affinity and ligand efficiency compared to the parent Isoniazid, suggesting its potential as a promising lead compound for anti‐tuberculosis drug development.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":"Article e70292"},"PeriodicalIF":2.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145986960","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}
2,2′-Biphenol-derived phosphoric acid is an effective catalyst for the dehydrative esterification of an equimolar mixture of carboxylic acids and alcohols in toluene at 100°C without the need to remove water from the reaction. The acidic P–OH and basic P ═ O moieties can work together effectively as a cooperative acid–base catalyst system. In this study, mechanistic insights into this catalytic reaction are obtained through experimental kinetics studies, density functional theory (DFT) calculations, and microkinetic simulations of 2,2′-biphenol-derived phosphoric acid and related catalysts. The kinetics and DFT analysis support a reaction mechanism that involves the formation of a phosphate–carboxylate complex and activation of the alcohol by the catalyst. The catalyst structure affects the reaction barrier of the dehydration step, thereby determining the overall activity. This step is further modulated by noncovalent interactions, including steric and π–π effects, which depend on the steric demand and flexibility of the catalyst backbone. Microkinetic simulations based on DFT-derived energy profiles successfully reproduce the experimentally observed conversion trends. Overall, the 2,2′-biphenol-derived phosphoric acid is found to have ideal properties for the catalysis of the present dehydrative esterification.
{"title":"Mechanistic Insights Into the 2,2′-Biphenol-Derived Phosphoric Acid–Catalyzed Dehydrative Esterification of Carboxylic Acids and Alcohols","authors":"Takeshi Yoshikawa, Hiroki Maekawara, Yuhei Monta, Takeshi Yamada, Ken Sakata, Manabu Hatano","doi":"10.1002/ajoc.70285","DOIUrl":"10.1002/ajoc.70285","url":null,"abstract":"<div>\u0000 \u0000 <p>2,2′-Biphenol-derived phosphoric acid is an effective catalyst for the dehydrative esterification of an equimolar mixture of carboxylic acids and alcohols in toluene at 100°C without the need to remove water from the reaction. The acidic P–OH and basic P ═ O moieties can work together effectively as a cooperative acid–base catalyst system. In this study, mechanistic insights into this catalytic reaction are obtained through experimental kinetics studies, density functional theory (DFT) calculations, and microkinetic simulations of 2,2′-biphenol-derived phosphoric acid and related catalysts. The kinetics and DFT analysis support a reaction mechanism that involves the formation of a phosphate–carboxylate complex and activation of the alcohol by the catalyst. The catalyst structure affects the reaction barrier of the dehydration step, thereby determining the overall activity. This step is further modulated by noncovalent interactions, including steric and π–π effects, which depend on the steric demand and flexibility of the catalyst backbone. Microkinetic simulations based on DFT-derived energy profiles successfully reproduce the experimentally observed conversion trends. Overall, the 2,2′-biphenol-derived phosphoric acid is found to have ideal properties for the catalysis of the present dehydrative esterification.</p>\u0000 </div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098591","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}
M. K. Mohamed, A. A. K. Mohammed, M. M. M. Aly, A.-A. M. Gaber, A. A. Saddik, “Synthesis, DFT Calculations, and Molecular Docking Study of New Aggregation-Induced Emission Lumiogens Based on Thieno[2,3-d]pyrimidine Moiety,” Asian Journal of Organic Chemistry 14, no. 3(2025): e202400670.
ABSTRACT
The discovery of novel Aggregation-Induced Emission (AIE) systems based on heterocyclic compounds holds significant potential. In this study, a series of new AIE systems based on thieno[2,3-d]pyrimidine moiety synthesized and characterized by spectroscopic analyses. These compounds exhibited weak emission in DMSO solution but displayed strong solid-state fluorescence at λmax = 556, 527, 527, and 515 nm for compounds 7 a, 7 b, 7 c, and 7 e respectively. Additionally, compound 10 exhibited emission at 480 nm in DMSO, which was red-shifted to 490 nm in the solid state. Furthermore, the AIE behavior for these compounds was investigated in different DMSO/H2O fractions. Compounds 7 a–c, 7 e, and 10 exhibits a typical AIE behavior since these compounds showed weak fluorescence intensity in pure DMSO but sharply increased while the water content reached 80 % in the case of compounds 7 a–c, and 7 e, and 90 % in compound 10. Moreover, Density Functional Theory (DFT) calculations supported the role of molecular packing and intermolecular interactions in modulating the luminescence properties. Molecular docking studies suggested the potential of these AIE compounds as anticancer agents. Compound 7 a exhibits a strong binding affinity of −9.6 kcal/mol for CDK-2 compared with abemaciclib, palbociclib, and ribociclib drugs, indicating its potential as a potent CDK-2 inhibitor.
In page 7, after the conclusion, Table 2, the compound number column, the number “7b, 7c, 7d, 7e, 7f” was incorrect. This should be “7a, 7b, 7c, 7d, 7e”
Incorrect is:
The correct one is:
We apologize for this error.
M. K.穆罕默德，A. A. K.穆罕默德，M. M. M.阿里，A. A. a。M. Gaber， A. A. Saddik，“基于Thieno[2,3-d]嘧啶基团的新型聚集诱导发光物质的合成、DFT计算和分子对接研究”，中国有机化学杂志，第14期，no。3 (2025): e202400670。摘要基于杂环化合物的新型聚集诱导发射（AIE）体系的发现具有重要的潜力。本研究合成了一系列基于噻吩[2,3-d]嘧啶片段的新型AIE体系，并用光谱分析对其进行了表征。化合物7a、7b、7c和7e在λmax = 556、527、527和515 nm处表现出较强的固态荧光。此外，化合物10在DMSO中表现出480 nm的发光，在固态中红移到490 nm。此外，研究了这些化合物在不同DMSO/H2O馏分中的AIE行为。化合物7a - c、7e和10表现出典型的AIE行为，在纯DMSO中荧光强度较弱，但当化合物7a - c和7e的含水量达到80%，化合物10达到90%时荧光强度急剧增加。此外，密度泛函理论（DFT）计算支持分子堆积和分子间相互作用在调节发光特性中的作用。分子对接研究表明，这些AIE化合物具有抗癌潜力。与abemaciclib、palbociclib和ribociclib药物相比，化合物7a对CDK-2表现出−9.6 kcal/mol的强结合亲和力，表明其可能是一种有效的CDK-2抑制剂。在第7页，结论后，表2，复数列，数字“7b, 7c, 7d, 7e, 7f”不正确。这应该是“7a, 7b, 7c, 7d, 7e”错误的是：正确的是：我们为这个错误道歉
{"title":"Correction to “Synthesis, DFT Calculations, and Molecular Docking Study of New Aggregation-Induced Emission Lumiogens Based on Thieno[2,3-d]pyrimidine Moiety”","authors":"","doi":"10.1002/ajoc.70278","DOIUrl":"https://doi.org/10.1002/ajoc.70278","url":null,"abstract":"<p>M. K. Mohamed, A. A. K. Mohammed, M. M. M. Aly, A.-A. M. Gaber, A. A. Saddik, “Synthesis, DFT Calculations, and Molecular Docking Study of New Aggregation-Induced Emission Lumiogens Based on Thieno[2,3-d]pyrimidine Moiety,” <i>Asian Journal of Organic Chemistry</i> 14, no. 3(2025): e202400670.</p><p>ABSTRACT</p><p>The discovery of novel Aggregation-Induced Emission (AIE) systems based on heterocyclic compounds holds significant potential. In this study, a series of new AIE systems based on thieno[2,3-<i>d</i>]pyrimidine moiety synthesized and characterized by spectroscopic analyses. These compounds exhibited weak emission in DMSO solution but displayed strong solid-state fluorescence at λ<sub>max</sub> = 556, 527, 527, and 515 nm for compounds <b>7 a</b>, <b>7 b</b>, <b>7 c</b>, and <b>7 e</b> respectively. Additionally, compound <b>10</b> exhibited emission at 480 nm in DMSO, which was red-shifted to 490 nm in the solid state. Furthermore, the AIE behavior for these compounds was investigated in different DMSO/H<sub>2</sub>O fractions. Compounds <b>7 a</b>–<b>c</b>, <b>7 e</b>, and <b>10</b> exhibits a typical AIE behavior since these compounds showed weak fluorescence intensity in pure DMSO but sharply increased while the water content reached 80 % in the case of compounds <b>7 a</b>–<b>c</b>, and <b>7 e</b>, and 90 % in compound <b>10</b>. Moreover, Density Functional Theory (DFT) calculations supported the role of molecular packing and intermolecular interactions in modulating the luminescence properties. Molecular docking studies suggested the potential of these AIE compounds as anticancer agents. Compound <b>7 a</b> exhibits a strong binding affinity of −9.6 kcal/mol for CDK-2 compared with abemaciclib, palbociclib, and ribociclib drugs, indicating its potential as a potent CDK-2 inhibitor.</p><p>In page 7, after the conclusion, Table 2, the compound number column, the number “7b, 7c, 7d, 7e, 7f” was incorrect. This should be “7a, 7b, 7c, 7d, 7e”</p><p>Incorrect is:</p><p></p><p>The correct one is:\u0000\u0000 </p><p>We apologize for this error.</p>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://aces.onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.70278","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145887260","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}
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