Dr. Isao Mizota , Keiji Oshima , Nozomi Hoshiai , Ayaki Yamamoto , Masaki Mitani , Rabbia Batool , Prof. Dr. Bo‐Tau Liu , Prof. Dr. Makoto Shimizu
{"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
{"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
{"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}
Dr. Toreshettahally R. Swaroop , Dr. Rajaghatta N. Suresh , Dr. Muddegowda Umashankara , Dr. Kanchugarakoppal S. Rangappa
{"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}
Juan Tian , Shimin Yang , Ying Peng , Mengyun Chen , Xin Chen , Xinyi Wang , Dayong Sang
{"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}
Leysan I. Gallyamova , Alfiya R. Bayguzina , Ilfir R. Ramazanov
{"title":"Synthesis of N‐,O‐,S‐Heterocyclic Spiroadamantanes by Condensation of Ketones with Bifunctional OH‐, NH‐, SH‐Acids under the Action of Copper‐Containing Catalysts","authors":"Leysan I. Gallyamova , Alfiya R. Bayguzina , Ilfir R. Ramazanov","doi":"10.1002/ajoc.202400276","DOIUrl":"10.1002/ajoc.202400276","url":null,"abstract":"<div><div>Synthesis of adamantyl‐containing cyclic ketals, spirooxazolidines, spiroimidazolidines, spirooxathiolanes, spirodithiolanes, spirooxazines, spirobenzodioxoles with high yields was carried out by condensation of adamantyl‐containing ketones (adamantanone, kemantan, diamantanone) with diols, 1,2‐ethanedithiol and 2‐mercaptoethanol, 1,2‐diaminoethane and 2‐aminoethanol under the action of copper‐containing catalysts. In the case of multigram‐scale reaction of adamant‐2‐one with 1,2‐propanediol, the amount of catalyst can be reduced to 0.1 mol %.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400276"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622345","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}
{"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}
Prof. Dr. Tsuyoshi Murata , Satsuki Doi , Rina Ishikawa , Prof. Dr. Ko Furukawa , Prof. Dr. Yasushi Morita
{"title":"π‐Expansion on a Polycyclic Stable Neutral Radical: Synthesis and Physical Properties of a Benz‐Annulated Trioxotriangulene","authors":"Prof. Dr. Tsuyoshi Murata , Satsuki Doi , Rina Ishikawa , Prof. Dr. Ko Furukawa , Prof. Dr. Yasushi Morita","doi":"10.1002/ajoc.202400690","DOIUrl":"10.1002/ajoc.202400690","url":null,"abstract":"<div><div>We report the synthesis of a benz‐annulated derivative of trioxotriangulene (<strong>TOT</strong>), a fused polycyclic organic neutral radical, and also the investigation on the electronic effects of π‐expansion. The neutral radical species was highly stable under air in both solution and solid states. Quantum chemical calculation suggested that the molecule has a completely planar molecular structure, and the electronic spin is widely delocalized throughout the π‐skeleton while maintaining three‐fold symmetry, which was experimentally supported by electronic spin resonance spectrum. The neutral radical also showed a strong π‐association ability comparable to that of <strong>TOT</strong> neutral radical derivatives.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400690"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622610","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}
{"title":"Photocatalytic Deoxygenative Alkylation with Alcohols via Xanthates or Thionocarbonates","authors":"Wei Luo , Zhong Chen , Prof. Dr. Bing Yu","doi":"10.1002/ajoc.202400627","DOIUrl":"10.1002/ajoc.202400627","url":null,"abstract":"<div><div>Recent advancements in photocatalytic strategies have expanded the range of alkylating agents, including alkyl carboxylic acids and saturated hydrocarbons. Notably, alcohols are preferred for their availability, stability, and safety compared to traditional alkylating reagents such as alkyl halides. This review summarizes recent developments in photocatalytic deoxygenative alkylation using alcohols, specifically through the formation of xanthates or thionocarbonates.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400627"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622706","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}
{"title":"Enantioselective Synthesis of 2‐Substituted 2‐Hydroxymethylaziridines by Copper‐Catalyzed Sulfonylative Desymmetrization of 2‐Amino‐1,3‐Diols","authors":"Kosuke Yamamoto , Eibu Sakata , Anri Uehara , Masami Kuriyama , Osamu Onomura","doi":"10.1002/ajoc.202400643","DOIUrl":"10.1002/ajoc.202400643","url":null,"abstract":"<div><div>An enantioselective protocol for the synthesis of 2‐hydroxymethylaziridines with a tetrasubstituted carbon stereocenter have been established through the copper‐catalyzed asymmetric desymmetrization of 2‐substituted 2‐amino‐1,3‐diol derivatives by monosulfonylation. The present transformation consists of a reaction sequence involving the enantioselective monosulfonylation of 2‐amino‐1,3‐diols and the intramolecular ring closure of the resultant monosulfonylated products, which provides an efficient and straightforward entry to optically active 2‐substituted 2‐hydroxymethylaziridines. The potential synthetic utility of the present reaction is exemplified by the derivatization of the obtained aziridines into a variety of nitrogen‐containing molecules such as amino alcohols and functionalized aziridine derivatives with high enantiopurities.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 3","pages":"Article e202400643"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622723","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}