Phenyl‐4‐pyridyl‐2,5‐dipyrimidinylmethane (1) has been synthesized in five steps from 5‐methylpyrimidine. The structural feature of 1 is the symmetry elements with respect to the 180° rotation of the aryl group along the central C−C bonds. Due to this structural feature, the compound 1 is expected the good crystallinity despite of the asymmetric molecular structure. The optical resolution of 1 was achieved by high performance liquid chromatography using chiral stationary phase (chiral HPLC). The circular dichroism (CD) spectra of the two fractions showed opposite signs. As expected, the X‐ray crystallographic analysis was successfully performed for both the racemic and enantiomerically pure crystals of 1, with the nitrogen atoms being unambiguously assigned in both cases. It was concluded the first‐eluted fraction in chiral HPLC was determined to be S configuration both by the CD calculation for reproducing the experimental CD spectrum and by the anomalous diffraction of X‐ray crystallographic analysis of enantiomerically pure 1.
{"title":"Synthesis, Chiroptical Properties, and Absolute Configuration Determination of Phenyl‐4‐pyridyl‐2,5‐dipyrimidinylmethane","authors":"Kouzou Matsumoto , Rina Tanaka , Kaori Miki , Akihito Konishi , Hiroyuki Kurata , Takashi Kubo , Gennaro Pescitelli , Koichi Matsuo , Tatsuo Nehira","doi":"10.1002/ajoc.202400577","DOIUrl":"10.1002/ajoc.202400577","url":null,"abstract":"<div><div>Phenyl‐4‐pyridyl‐2,5‐dipyrimidinylmethane (<strong>1</strong>) has been synthesized in five steps from 5‐methylpyrimidine. The structural feature of <strong>1</strong> is the symmetry elements with respect to the 180° rotation of the aryl group along the central C−C bonds. Due to this structural feature, the compound <strong>1</strong> is expected the good crystallinity despite of the asymmetric molecular structure. The optical resolution of <strong>1</strong> was achieved by high performance liquid chromatography using chiral stationary phase (chiral HPLC). The circular dichroism (CD) spectra of the two fractions showed opposite signs. As expected, the X‐ray crystallographic analysis was successfully performed for both the racemic and enantiomerically pure crystals of <strong>1</strong>, with the nitrogen atoms being unambiguously assigned in both cases. It was concluded the first‐eluted fraction in chiral HPLC was determined to be <em>S</em> configuration both by the CD calculation for reproducing the experimental CD spectrum and by the anomalous diffraction of X‐ray crystallographic analysis of enantiomerically pure <strong>1</strong>.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 1","pages":"Article e202400577"},"PeriodicalIF":2.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113151","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}
s‐Tetrazines are aromatic heterocyclic systems with distinct structural and optoelectronic features, which have led to the design and development of tetrazine‐derived systems in various applications. In this review, we summarize all the research reported on the subject of the applicability of tetrazine derivatives for photocatalytic chemical transformation, hydrogen production, and coordination‐based analyte detection.
{"title":"Functional 1,2,4,5‐Tetrazine Systems for Photocatalysis and Sensing","authors":"K. Aswani Raj , M. Rajeswara Rao","doi":"10.1002/ajoc.202400553","DOIUrl":"10.1002/ajoc.202400553","url":null,"abstract":"<div><div>s‐Tetrazines are aromatic heterocyclic systems with distinct structural and optoelectronic features, which have led to the design and development of tetrazine‐derived systems in various applications. In this review, we summarize all the research reported on the subject of the applicability of tetrazine derivatives for photocatalytic chemical transformation, hydrogen production, and coordination‐based analyte detection.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 1","pages":"Article e202400553"},"PeriodicalIF":2.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143114351","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}
Chaolin Wu , Yanlong Xie , Dr. Jiliang Song , Prof. Xiujuan Feng , Siqi Jian , Wenchao Lu , Jiuzhen Zhu , Prof. Yoshinori Yamamoto , Prof. Ming Bao
The palladium‐catalyzed three‐component coupling of aryl (hetero) methylsulfonamide, allyltributyltin and carbon dioxide (carboxylative Stille coupling reaction) was successfully conduced to produce β,γ‐unsaturated esters in satisfactory to good yields. The reaction was carried out under mild conditions by using in situ generated palladium nanoparticles as catalyst through the formation of π‐allylpalladium sulfonamide intermediates in the presence of tetrabutylammonium bromide (TBAB).
{"title":"Caboxylative Coupling of N‐(Arylmethyl)sulfonimides with Allyltributylstannane Catalyzed by Palladium Nanoparticles Involving Benzylic C−N Cleavage","authors":"Chaolin Wu , Yanlong Xie , Dr. Jiliang Song , Prof. Xiujuan Feng , Siqi Jian , Wenchao Lu , Jiuzhen Zhu , Prof. Yoshinori Yamamoto , Prof. Ming Bao","doi":"10.1002/ajoc.202400388","DOIUrl":"10.1002/ajoc.202400388","url":null,"abstract":"<div><div>The palladium‐catalyzed three‐component coupling of aryl (hetero) methylsulfonamide, allyltributyltin and carbon dioxide (carboxylative Stille coupling reaction) was successfully conduced to produce <em>β</em>,<em>γ</em>‐unsaturated esters in satisfactory to good yields. The reaction was carried out under mild conditions by using in situ generated palladium nanoparticles as catalyst through the formation of π‐allylpalladium sulfonamide intermediates in the presence of tetrabutylammonium bromide (TBAB).</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 1","pages":"Article e202400388"},"PeriodicalIF":2.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143115160","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}
Shikha Pandey , Arsala Kamal , Ambuj Kumar Kushwaha , Dr. Sundaram Singh
In the current study, for the first time, N‐phenylazo (triazine) derivatives of 6‐aminouracil compounds were produced at room temperature under catalyst‐free conditions in pyridine using an easy, efficient, and green process. The main advantages of this approach are that it doesn't require a catalyst, is inexpensive, eco‐friendly, non‐toxic, and simple to handle. This technique shows a broad range of substrate compatibility for uracil compounds and diazonium salts.
{"title":"Synthesis of N‐Phenylazo (Triazine) Derivatives of 6‐Aminouracil Using Diazonium Salt Under Catalyst‐Free Condition","authors":"Shikha Pandey , Arsala Kamal , Ambuj Kumar Kushwaha , Dr. Sundaram Singh","doi":"10.1002/ajoc.202400409","DOIUrl":"10.1002/ajoc.202400409","url":null,"abstract":"<div><div>In the current study, for the first time, N‐phenylazo (triazine) derivatives of 6‐aminouracil compounds were produced at room temperature under catalyst‐free conditions in pyridine using an easy, efficient, and green process. The main advantages of this approach are that it doesn't require a catalyst, is inexpensive, eco‐friendly, non‐toxic, and simple to handle. This technique shows a broad range of substrate compatibility for uracil compounds and diazonium salts.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 1","pages":"Article e202400409"},"PeriodicalIF":2.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143116239","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 palladium‐catalyzed dehydrogenative cross‐coupling reactions between silanes and oxygen‐containing functional groups (water, alcohols, phenols) to generate the corresponding silanols, monosilane ethers, and disilane ethers directly in moderate to high yields. This strategy does not rely on any additional oxidizing agents or proton reductants. The possible mechanisms for this transformation are also proposed.
{"title":"Palladium‐Catalyzed Dehydrogenation Cross‐Coupling Reactions of Hydrosilanes: Facile Synthesis of Silanols and Silyl Ethers","authors":"Lianji Zhang , Yujuan Wu , Cuiping Wang , Yuhui Zhao , Wanguo Wei , Zhiqiang Zhang","doi":"10.1002/ajoc.202400471","DOIUrl":"10.1002/ajoc.202400471","url":null,"abstract":"<div><div>A palladium‐catalyzed dehydrogenative cross‐coupling reactions between silanes and oxygen‐containing functional groups (water, alcohols, phenols) to generate the corresponding silanols, monosilane ethers, and disilane ethers directly in moderate to high yields. This strategy does not rely on any additional oxidizing agents or proton reductants. The possible mechanisms for this transformation are also proposed.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 1","pages":"Article e202400471"},"PeriodicalIF":2.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143117390","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}
Weeds are problematic plant species around the world. Various strategies exist for controlling weeds, but chemical treatment remains the preferred method, particularly when using natural substances. In this research, a crude aqueous‐methanol extract from dried Zanthoxylum limonella fruits was acid‐base partitioned into four fractions: neutral extract (NE), acid extract (AE), basic extract (BE), and aqueous extract (AQ). These fractions were further separated into seventeen subfractions: NEF1 to NEF7, AEF1 to AEF5, and BEF1 to BEF5, which were then tested for herbicidal activity against the growth of Chinese amaranth (Amaranthus tricolor) and barnyard grass (Echinochloa crus‐galli). Active subfractions were isolated via column chromatography and identified using spectroscopic methods, yielding seven active compounds: xanthoxyline (1), tambulin (2), atanine (3), prudomestin (4), skimmianine (5), p‐methoxybenzoic acid (6), and methyl caffeate (7). Compounds 2–7 had not been previously reported in Z. limonella. Xanthoxyline (1) was identified as the most potent botanical herbicide, fully inhibiting seed germination of Chinese amaranth and barnyard grass. This compound also decreased seed imbibition and α‐amylase activity in both species. Molecular docking studies on the α‐amylase enzyme (PDB ID: 1BG9) revealed that the aromatic, hydroxy, and carbonyl groups of xanthoxyline (1) interact with the enzyme's active sites.
{"title":"Bioassay‐Guided Extraction and Isolation of Natural Herbicides from Dried Zanthoxylum limonella Alston Fruits","authors":"Warot Chotpatiwetchkul , Patchanee Charoenying , Montinee Teerarak , Jatuporn Meesin , Nathjanan Jongkon , Nawasit Chotsaeng , Chamroon Laosinwattana","doi":"10.1002/ajoc.202400317","DOIUrl":"10.1002/ajoc.202400317","url":null,"abstract":"<div><div>Weeds are problematic plant species around the world. Various strategies exist for controlling weeds, but chemical treatment remains the preferred method, particularly when using natural substances. In this research, a crude aqueous‐methanol extract from dried <em>Zanthoxylum limonella</em> fruits was acid‐base partitioned into four fractions: neutral extract (NE), acid extract (AE), basic extract (BE), and aqueous extract (AQ). These fractions were further separated into seventeen subfractions: NEF1 to NEF7, AEF1 to AEF5, and BEF1 to BEF5, which were then tested for herbicidal activity against the growth of Chinese amaranth (<em>Amaranthus tricolor</em>) and barnyard grass (<em>Echinochloa crus‐galli</em>). Active subfractions were isolated via column chromatography and identified using spectroscopic methods, yielding seven active compounds: xanthoxyline (<strong>1</strong>), tambulin (<strong>2</strong>), atanine (<strong>3</strong>), prudomestin (<strong>4</strong>), skimmianine (<strong>5</strong>), <em>p</em>‐methoxybenzoic acid (<strong>6</strong>), and methyl caffeate (<strong>7</strong>). Compounds <strong>2–7</strong> had not been previously reported in <em>Z. limonella</em>. Xanthoxyline (<strong>1</strong>) was identified as the most potent botanical herbicide, fully inhibiting seed germination of Chinese amaranth and barnyard grass. This compound also decreased seed imbibition and α‐amylase activity in both species. Molecular docking studies on the α‐amylase enzyme (PDB ID: 1BG9) revealed that the aromatic, hydroxy, and carbonyl groups of xanthoxyline (<strong>1</strong>) interact with the enzyme's active sites.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 1","pages":"Article e202400317"},"PeriodicalIF":2.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143119175","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}
In article number e202400547, Tomoya Takao, Atsushi Kawamura, and Hidefumi Makabe accomplished the first total synthesis of inaoside A, isolated from the edible mushroom Laetiporus cremeiporus, using α-selective Schmidt glycosylation of the easily prepared 2,3,5-tri-TBS-protected ribofuranosyl trichloroacetimidate as a key step. In this cover picture, the creatures of L. cremeiours are trying to build inaoside by guiding the aglycon to the α-face of the ribose derivative.
{"title":"Front Cover: First Total Synthesis of Inaoside A (Asian J. Org. Chem. 12/2024)","authors":"Tomoya Takao, Atsushi Kawamura, Hidefumi Makabe","doi":"10.1002/ajoc.202481201","DOIUrl":"https://doi.org/10.1002/ajoc.202481201","url":null,"abstract":"<p>In article number e202400547, Tomoya Takao, Atsushi Kawamura, and Hidefumi Makabe accomplished the first total synthesis of inaoside A, isolated from the edible mushroom <i>Laetiporus cremeiporus</i>, using α-selective Schmidt glycosylation of the easily prepared 2,3,5-tri-TBS-protected ribofuranosyl trichloroacetimidate as a key step. In this cover picture, the creatures of <i>L. cremeiours</i> are trying to build inaoside by guiding the aglycon to the α-face of the ribose derivative.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 12","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202481201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142861224","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}
The natural product quinine has been known to humankind for centuries, and in that time has played a pivotal role in the treatment of malaria. Quinine, and the related cinchona alkaloids, have seen widespread contemporary use across chemical and biological disciplines, owing in part to the plethora of functional groups and stereochemical information contained within their scaffold. This review focuses on site‐selective synthetic modifications of the cinchona alkaloids. Our comparative analysis may act as a ‘user manual’ for the selective functionalisation of the cinchona alkaloids, and aims to promote consideration of remarkable and lesser‐understood aspects of cinchona chemistry.
{"title":"Site‐Selective Synthetic Modifications of the Cinchona Alkaloids","authors":"Finlay P. Player , Daniel J. Foley","doi":"10.1002/ajoc.202400397","DOIUrl":"10.1002/ajoc.202400397","url":null,"abstract":"<div><div>The natural product quinine has been known to humankind for centuries, and in that time has played a pivotal role in the treatment of malaria. Quinine, and the related cinchona alkaloids, have seen widespread contemporary use across chemical and biological disciplines, owing in part to the plethora of functional groups and stereochemical information contained within their scaffold. This review focuses on site‐selective synthetic modifications of the cinchona alkaloids. Our comparative analysis may act as a ‘user manual’ for the selective functionalisation of the cinchona alkaloids, and aims to promote consideration of remarkable and lesser‐understood aspects of cinchona chemistry.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 12","pages":"Article e202400397"},"PeriodicalIF":2.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142860655","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}
Herein an efficient method for in situ generated o–quinone methides without essential electronic or steric groups at the exocyclic methylene or on six‐membered ring was established. The method relies on acetylation of salicylylols and subsequently base promoted 1,4‐elimination. The in situ generated o–quinone methides could be undergoing conjugate addition with 3‐aryl oxindoles in one‐pot reaction system, which provided 3,3‐disubstituted oxindoles bearing a quaternary stereocenter in good yields (up to 99 %).
{"title":"Conjugate Addition of 3‐Aryl Oxindoles to In Situ Generated o–Quinone Methides Without Essential Electronic or Steric Groups","authors":"Liu Song","doi":"10.1002/ajoc.202400370","DOIUrl":"10.1002/ajoc.202400370","url":null,"abstract":"<div><div>Herein an efficient method for <em>in situ</em> generated <em>o</em>–quinone methides without essential electronic or steric groups at the exocyclic methylene or on six‐membered ring was established. The method relies on acetylation of salicylylols and subsequently base promoted 1,4‐elimination. The <em>in situ</em> generated <em>o</em>–quinone methides could be undergoing conjugate addition with 3‐aryl oxindoles in one‐pot reaction system, which provided 3,3‐disubstituted oxindoles bearing a quaternary stereocenter in good yields (up to 99 %).</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 12","pages":"Article e202400370"},"PeriodicalIF":2.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142860748","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}
Microwave synthesis is a sustainable and eco‐friendly method for producing novel organic compounds, offering faster reactions, higher yields, and improved purity compared to traditional techniques. Efficiency is increased by the uniform heating caused by microwave radiation, especially for the synthesis of heterocyclic compound and their derivatives. Owing to have important biological and therapeutic qualities, a number of microwave‐assisted synthetic methods of pyrroles have been developed that produce better results than the conventional reported method. In view of this, the present review emphasizes solvent‐free and catalyst‐free methods for the microwave‐assisted synthesis of pyrrole and its fusion with other heterocycles such as furan, pyridine, beta‐lactam, and indole. A comparison between traditional and microwave‐assisted techniques is given in terms of reagents, covering yield, waste minimization, solvents, and catalysts.
{"title":"Microwave‐Assisted Synthetic Pathways of Pyrrole: A Comprehensive Review","authors":"Ritika Yadav , Mohit Sanduja , Vinod Kumar , Kirti Sharma , Sameer Khan , Kapil Kumar","doi":"10.1002/ajoc.202400401","DOIUrl":"10.1002/ajoc.202400401","url":null,"abstract":"<div><div>Microwave synthesis is a sustainable and eco‐friendly method for producing novel organic compounds, offering faster reactions, higher yields, and improved purity compared to traditional techniques. Efficiency is increased by the uniform heating caused by microwave radiation, especially for the synthesis of heterocyclic compound and their derivatives. Owing to have important biological and therapeutic qualities, a number of microwave‐assisted synthetic methods of pyrroles have been developed that produce better results than the conventional reported method. In view of this, the present review emphasizes solvent‐free and catalyst‐free methods for the microwave‐assisted synthesis of pyrrole and its fusion with other heterocycles such as furan, pyridine, beta‐lactam, and indole. A comparison between traditional and microwave‐assisted techniques is given in terms of reagents, covering yield, waste minimization, solvents, and catalysts.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 12","pages":"Article e202400401"},"PeriodicalIF":2.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142861165","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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