The use of attractive noncovalent interactions is emerging as a versatile approach to address site‐selectivity challenges. Herein, we report ortho‐selective Suzuki coupling reactions in water of 2,3‐dichloroarenes and 2,4‐dichloroarenes bearing a hydroxy group in the presence of a palladacycle catalyst and directed by noncovalent interactions. Various ortho‐substituted arylphenols and arylbenzyl alcohols were obtained in good to excellent yields with high selectivity. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations suggested that the ortho‐selective Suzuki coupling of dichlorophenols and dichlorobenzyl alcohols occurred through electrostatic interactions and hydrogen bonding interactions, respectively.
{"title":"ortho‐Selective Suzuki Coupling of Dichlorophenol and Dichlorobenzylalcohol in Water under Palladium Catalysis Directed by Noncovalent Interactions and Computational Analysis","authors":"Shangxun Zhao , Shuo Wen , Hongrun Chen , Kewei Zhan , Jiawei Weng , Danli Ding , Xingwei Cai , Heng Song , Chen Xu","doi":"10.1002/ajoc.202400581","DOIUrl":"10.1002/ajoc.202400581","url":null,"abstract":"<div><div>The use of attractive noncovalent interactions is emerging as a versatile approach to address site‐selectivity challenges. Herein, we report ortho‐selective Suzuki coupling reactions in water of 2,3‐dichloroarenes and 2,4‐dichloroarenes bearing a hydroxy group in the presence of a palladacycle catalyst and directed by noncovalent interactions. Various ortho‐substituted arylphenols and arylbenzyl alcohols were obtained in good to excellent yields with high selectivity. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations suggested that the <em>ortho</em>‐selective Suzuki coupling of dichlorophenols and dichlorobenzyl alcohols occurred through electrostatic interactions and hydrogen bonding interactions, respectively.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400581"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622430","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}
Yulong Zhang , Hang Wang , Bin Gu , Bowen Hu , Dr. Xiaoxue Tang , Prof. Dr. Yushuang Chen
A new iron catalytic conjugate reduction of exocyclic α,β‐unsaturated carbonyl compounds with PMHS has been established for the first time. The reaction utilized PMHS as readily available, non‐toxic, and mild reductant that can be handled in open air. This protocol exhibits high compatibility with various substituents, and gives excellent yields, providing an environmentally benign and efficient access to construct synthetically useful α‐benzyl cyclic ketone scaffolds.
{"title":"FeCl3‐Promoted Conjugate Reduction of Exocyclic α,β‐Unsaturated Ketones with Polymethylhydrosiloxane","authors":"Yulong Zhang , Hang Wang , Bin Gu , Bowen Hu , Dr. Xiaoxue Tang , Prof. Dr. Yushuang Chen","doi":"10.1002/ajoc.202400691","DOIUrl":"10.1002/ajoc.202400691","url":null,"abstract":"<div><div>A new iron catalytic conjugate reduction of exocyclic α,β‐unsaturated carbonyl compounds with PMHS has been established for the first time. The reaction utilized PMHS as readily available, non‐toxic, and mild reductant that can be handled in open air. This protocol exhibits high compatibility with various substituents, and gives excellent yields, providing an environmentally benign and efficient access to construct synthetically useful α‐benzyl cyclic ketone scaffolds.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400691"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622447","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}
Boroxines, six‐membered heterocyclic compounds with alternating O and B atoms, are readily formed by dehydration of boronic acids, while it is also known to be readily hydrolyzed to boronic acids under wet conditions. Therefore, hydrolysis is one of major problems for boroxine‐based architectures and materials, although they have self‐healing properties that can be restored simply by dehydration. In recent years, interesting studies have been reported to improve the hydrostability of boroxines, with some boroxines being stable even in water. This review categorizes and summarizes the findings on the enhancement of the hydrostability of boroxines according to the methods used.
{"title":"Hydrostability of Boroxines","authors":"Dr. Kosuke Ono","doi":"10.1002/ajoc.202400683","DOIUrl":"10.1002/ajoc.202400683","url":null,"abstract":"<div><div>Boroxines, six‐membered heterocyclic compounds with alternating O and B atoms, are readily formed by dehydration of boronic acids, while it is also known to be readily hydrolyzed to boronic acids under wet conditions. Therefore, hydrolysis is one of major problems for boroxine‐based architectures and materials, although they have self‐healing properties that can be restored simply by dehydration. In recent years, interesting studies have been reported to improve the hydrostability of boroxines, with some boroxines being stable even in water. This review categorizes and summarizes the findings on the enhancement of the hydrostability of boroxines according to the methods used.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400683"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622726","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}
Mónica G. Flores‐Amaro , María C. García‐López , David A. Velázquez Hernández , Horacio Reyes‐Pérez , Valeria Villarreal‐García , Rosa Martha Jiménez‐Barrera , Rodrigo Chan‐Navarro , Vianey González‐Villasana , Diana Reséndez‐Pérez.
In this work, we report a blue‐LED self‐assembly‐assisted synthesis of novel emissive organoboron esters, achieved in just 30 minutes with quantitative yields. The molecular structure in solution (characterized by 1H and 11B NMR, and mass spectrometry) was further confirmed via X‐ray molecular diffraction analysis for compound 3, where the boron ion adopts a distorted tetrahedral geometry. The photophysical properties of these molecules were analyzed in solution, revealing that 1, featuring tert‐butyl groups and boron heterocycles with a nitro‐substituent, exhibits superior photostability compared to its derivatives. Photobleaching values showed an inverse correlation with the oxidation potentials of compounds 1–3, except for 4, used as a reference. Mass spectrometry further revealed greater energetic stability of the molecular ion of 1. Notably, compound 3 demonstrated good solubility, high photostability, and adequate biocompatibility, making it a promising fluorescent dye for biomedical applications. Cytotoxicity assays in HEK‐293 cells across different concentrations confirmed its non‐toxic nature. Theoretical calculations further supported the high chemical stability of all compounds, attributing it to a synergistic interaction between electronic and steric effects, which protect the fluorophores by substitution of Schiff bases and formation of boron heterocycles. Additionally, 3 exhibited strong, non‐hazardous blue fluorescence when tested on HEK‐293 and MDA‐MB‐231 cells.
{"title":"Blue‐LED Self‐Assembly‐Assisted Synthesis of New Photostable Organoboron Esters for Live‐Cell Imaging","authors":"Mónica G. Flores‐Amaro , María C. García‐López , David A. Velázquez Hernández , Horacio Reyes‐Pérez , Valeria Villarreal‐García , Rosa Martha Jiménez‐Barrera , Rodrigo Chan‐Navarro , Vianey González‐Villasana , Diana Reséndez‐Pérez.","doi":"10.1002/ajoc.202400613","DOIUrl":"10.1002/ajoc.202400613","url":null,"abstract":"<div><div>In this work, we report a blue‐LED self‐assembly‐assisted synthesis of novel emissive organoboron esters, achieved in just 30 minutes with quantitative yields. The molecular structure in solution (characterized by <sup>1</sup>H and <sup>11</sup>B NMR, and mass spectrometry) was further confirmed via X‐ray molecular diffraction analysis for compound <strong>3</strong>, where the boron ion adopts a distorted tetrahedral geometry. The photophysical properties of these molecules were analyzed in solution, revealing that <strong>1</strong>, featuring <em>tert</em>‐butyl groups and boron heterocycles with a nitro‐substituent, exhibits superior photostability compared to its derivatives. Photobleaching values showed an inverse correlation with the oxidation potentials of compounds <strong>1</strong>–<strong>3</strong>, except for <strong>4</strong>, used as a reference. Mass spectrometry further revealed greater energetic stability of the molecular ion of <strong>1</strong>. Notably, compound <strong>3</strong> demonstrated good solubility, high photostability, and adequate biocompatibility, making it a promising fluorescent dye for biomedical applications. Cytotoxicity assays in HEK‐293 cells across different concentrations confirmed its non‐toxic nature. Theoretical calculations further supported the high chemical stability of all compounds, attributing it to a synergistic interaction between electronic and steric effects, which protect the fluorophores by substitution of Schiff bases and formation of boron heterocycles. Additionally, <strong>3</strong> exhibited strong, non‐hazardous blue fluorescence when tested on HEK‐293 and MDA‐MB‐231 cells.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400613"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622660","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. Jira Jongcharoenkamol , Rujiporn Saewa , Atchariya Intasri , Pariya Atawong , Phanupong Changtor , Dr. Kittisak Buddhachat , Dr. Sutthichat Kerdphon
A facile green synthesis of the anti‐inflammatory gene expression of 4H‐3,1‐benzoxazine was developed under a commercial copper catalytic system. Benzoxazines were synthesized from 2‐aminobenzyl alcohols and aromatic aldehydes including heterocyclic aromatic aldehydes using an economical commercially available copper(I)iodide (CuI) as a catalyst in the presence of the base, tBuOK. Target products were achieved in moderate to high yields with up to 75 % isolated yield. 4H‐3,1‐Benzoxazine enabled down‐regulation of inflammatory gene expression including tumor necrosis factor‐α (TNF‐α), inducible nitric oxide synthase (iNOS), cyclooxygenase‐2 (COX‐2), and interleukin‐1β (IL‐1β) in the lipopolysaccharide (LPS)‐stimulated RAW 264.7 macrophage cell line using a real‐time quantitative polymerase chain reaction (RT‐qPCR) comparable to anti‐inflammatory drug, dexamethasone. These results demonstrated that 4H‐3,1‐Benzoxazines possess the potential capability of anti‐inflammation.
{"title":"Commercial Copper‐Catalyzed Aerobic Oxidative Synthesis of 4H‐3,1‐Benzoxazine and Their Effects on Anti‐Inflammatory Genes Expression","authors":"Dr. Jira Jongcharoenkamol , Rujiporn Saewa , Atchariya Intasri , Pariya Atawong , Phanupong Changtor , Dr. Kittisak Buddhachat , Dr. Sutthichat Kerdphon","doi":"10.1002/ajoc.202400609","DOIUrl":"10.1002/ajoc.202400609","url":null,"abstract":"<div><div>A facile green synthesis of the anti‐inflammatory gene expression of 4<em>H</em>‐3,1‐benzoxazine was developed under a commercial copper catalytic system. Benzoxazines were synthesized from 2‐aminobenzyl alcohols and aromatic aldehydes including heterocyclic aromatic aldehydes using an economical commercially available copper(I)iodide (CuI) as a catalyst in the presence of the base, <sup><em>t</em></sup>BuOK. Target products were achieved in moderate to high yields with up to 75 % isolated yield. 4<em>H</em>‐3,1‐Benzoxazine enabled down‐regulation of inflammatory gene expression including tumor necrosis factor‐α (TNF‐<em>α</em>), inducible nitric oxide synthase (iNOS), cyclooxygenase‐2 (COX‐2), and interleukin‐1<em>β</em> (IL‐1<em>β</em>) in the lipopolysaccharide (LPS)‐stimulated RAW 264.7 macrophage cell line using a real‐time quantitative polymerase chain reaction (RT‐qPCR) comparable to anti‐inflammatory drug, dexamethasone. These results demonstrated that 4<em>H</em>‐3,1‐Benzoxazines possess the potential capability of anti‐inflammation.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400609"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622363","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}
Prof. Dr. Takanori Suzuki , Dr. Wataru Nojo , Yuiki Kawada , Soichiro Sugiyama , Takaya Ikeuchi , Prof. Dr. Yusuke Ishigaki , Prof. Dr. Hiroaki Ohno
The Wurster's Blue skeleton embedded in an axially chiral indolo[2,3‐c]carbazole framework can act as a key chromophore to realize three‐way‐output electrochromic response (UV‐Vis‐near IR absorption, fluorescence, and circular dichroism) upon reversible electrochemical interconversion with the corresponding neutral electron donor, which was effectively synthesized by gold(I)‐catalyzed cascade cyclization of 2‐azidophenyl‐1,3‐butadiyne with a 2‐phenyl‐1‐naphthyl terminal group.
{"title":"Gold(I)‐catalyzed Synthesis of Axially Chiral Indolo[2,3‐c]carbazole Exhibiting Advanced Electrochromic Response","authors":"Prof. Dr. Takanori Suzuki , Dr. Wataru Nojo , Yuiki Kawada , Soichiro Sugiyama , Takaya Ikeuchi , Prof. Dr. Yusuke Ishigaki , Prof. Dr. Hiroaki Ohno","doi":"10.1002/ajoc.202400695","DOIUrl":"10.1002/ajoc.202400695","url":null,"abstract":"<div><div>The Wurster's Blue skeleton embedded in an axially chiral indolo[2,3‐<em>c</em>]carbazole framework can act as a key chromophore to realize three‐way‐output electrochromic response (UV‐Vis‐near IR absorption, fluorescence, and circular dichroism) upon reversible electrochemical interconversion with the corresponding neutral electron donor, which was effectively synthesized by gold(I)‐catalyzed cascade cyclization of 2‐azidophenyl‐1,3‐butadiyne with a 2‐phenyl‐1‐naphthyl terminal group.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400695"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622365","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}
Vinay S. Sharma, Saloni Mishra, Anuj S. Sharma, Neha Sharma, Rajender S. Varma, Pranav S. Shrivastav, Achalkumar Ammathnadu Sudhakar
The cover design illustrates the applicability of microcrystalline cellulose and cellulose nanocrystals in organic transformations. In the illustration, an organic chemist is excited to explore the wide potential of these commercially viable materials in various sustainable organic reactions within the green forest of cellulose. Microcrystalline cellulose and cellulose nanocrystals offer high catalytic efficiency and selectivity in organic reactions, promoting greener and more sustainable processes. The biocompatibility and renewable nature of these materials attract the attention of organic chemists, especially when compared to traditional catalysts. More details can be found inarticle number e202400586 by Pranav S. Shrivastav, Achalkumar Ammathnadu Sudhakar, and co-workers.