An efficient method for the activation of non‐activated cyclopropyl esters is developed using a hypervalent iodine(III) species and Selectfluor for the generation of acyl fluoride intermediates. The reactive acyl fluoride intermediate is smoothly transformed into various functional groups such as amides, esters, thioesters, and ketones depending on the nucleophile used in the in‐situ transformation. Utilizing the oxidation process of an iodoarene by Selectfluor, the activation is improved from a stoichiometric to catalytic protocol. Furthermore, the activation is employed in the chemoselective activation of target cyclopropyl ester in the presence of other ester moieties.
{"title":"Metal‐Free Generation of Acyl Fluorides via Activation of Cyclopropyl Esters using a Hypervalent Iodine(III) Species and Selectfluor.","authors":"Eun-sol Choi, Hyo-Jun Lee, Maruoka Keiji","doi":"10.1002/ajoc.202400398","DOIUrl":"https://doi.org/10.1002/ajoc.202400398","url":null,"abstract":"An efficient method for the activation of non‐activated cyclopropyl esters is developed using a hypervalent iodine(III) species and Selectfluor for the generation of acyl fluoride intermediates. The reactive acyl fluoride intermediate is smoothly transformed into various functional groups such as amides, esters, thioesters, and ketones depending on the nucleophile used in the in‐situ transformation. Utilizing the oxidation process of an iodoarene by Selectfluor, the activation is improved from a stoichiometric to catalytic protocol. Furthermore, the activation is employed in the chemoselective activation of target cyclopropyl ester in the presence of other ester moieties.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217006","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}
Wenbo Ma, Tao Zheng, Zihan Yu, Junlong Li, Qilin Gu, Linghui Gu, Zheyu Li
A mechanochemical cross‐dehydrogenative coupling reaction of pyrazolones with thiols using ball milling is described. Benzeneselenol and dichalcogenide substrates are also compatible under mild reaction conditions, yielding up to 99%. Notable features of this reaction include its metal‐ and solvent‐free, wide substrate scope and good functional group tolerance. Preliminary mechanistic investigations suggest that a radical pathway is likely involved in this C‒H chalcogenation reaction
{"title":"Solvent‐Free Dehydrogenative C‒H Chalcogenations of Pyrazolones Using Mechanochemistry","authors":"Wenbo Ma, Tao Zheng, Zihan Yu, Junlong Li, Qilin Gu, Linghui Gu, Zheyu Li","doi":"10.1002/ajoc.202400353","DOIUrl":"https://doi.org/10.1002/ajoc.202400353","url":null,"abstract":"A mechanochemical cross‐dehydrogenative coupling reaction of pyrazolones with thiols using ball milling is described. Benzeneselenol and dichalcogenide substrates are also compatible under mild reaction conditions, yielding up to 99%. Notable features of this reaction include its metal‐ and solvent‐free, wide substrate scope and good functional group tolerance. Preliminary mechanistic investigations suggest that a radical pathway is likely involved in this C‒H chalcogenation reaction","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142216970","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}
Twelve thiazole hybrids (2a‐2l) were synthesized in this study incorporating with Schiff base and carbazole scaffolds and characterized by spectral analyses. Antimicrobial activity and antioxidant potency were investigated by agar disc diffusion method and DPPH free radical scavenging assays where trimethyldihydrothiazole 2c had revealed its higher efficacy in both biological studies. It had displayed IC50 of 25.55 ± 0.40 µg/mL which is higher than the standard ascorbic acid (IC50 = 41.31 ± 1.83 µg/mL) as well as dihydrothiazoylchromenone 2e showed promising antioxidant activity with IC50 value of 40.82 ± 0.54. The compound 2c satisfied all the ADME properties and toxicological parameters with maximum drug score value (0.39) among all derivatives. Molecular docking was undertaken for higher bioactive compounds where 2c revealed its wide range of interactions with different amino acid residues which was also endorsed with the output of molecular dynamics simulation.
{"title":"Synthesis, antimicrobial and antioxidant activity with in silico ADMET prediction, molecular docking and dynamics studies of carbazole ring containing thiazole Schiff bases","authors":"Sumita Saznin Marufa, Mohammad Mostafizur Rahman, Md. Mizanur Rahman, Rownok Jahan, Gulshan Ara, Hiroshi Nishino, Mohammad Sayed Alam, Md. Aminul Haque","doi":"10.1002/ajoc.202400363","DOIUrl":"https://doi.org/10.1002/ajoc.202400363","url":null,"abstract":"Twelve thiazole hybrids (2a‐2l) were synthesized in this study incorporating with Schiff base and carbazole scaffolds and characterized by spectral analyses. Antimicrobial activity and antioxidant potency were investigated by agar disc diffusion method and DPPH free radical scavenging assays where trimethyldihydrothiazole 2c had revealed its higher efficacy in both biological studies. It had displayed IC50 of 25.55 ± 0.40 µg/mL which is higher than the standard ascorbic acid (IC50 = 41.31 ± 1.83 µg/mL) as well as dihydrothiazoylchromenone 2e showed promising antioxidant activity with IC50 value of 40.82 ± 0.54. The compound 2c satisfied all the ADME properties and toxicological parameters with maximum drug score value (0.39) among all derivatives. Molecular docking was undertaken for higher bioactive compounds where 2c revealed its wide range of interactions with different amino acid residues which was also endorsed with the output of molecular dynamics simulation.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217008","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 dearomative addition of readily available carboranyllithium reagents to isoquinolinium salts gave a series of carborane cage C‐substituted 1,2‐dihydroisoquinolines in 43−85% yields. Subsequent hydrogenation enabled the facile synthesis of corresponding carboranyl 1,2,3,4‐tetrahydroisoquinolines in 65−95% yields. The addition‐reduction pathway is applicable to a wide range of substituted isoquinolinium salts and o‐carborane or m‐carborane.
将容易获得的硼烷基锂试剂与异喹啉盐进行脱芳加成，可得到一系列硼烷笼 C 取代的 1,2-二氢异喹啉，收率为 43-85%。随后的氢化反应使相应的 1,2,3,4-四氢异喹啉的硼烷合成变得容易，产率达到 65-95%。加成-还原途径适用于多种取代的异喹啉盐和邻硼烷或间硼烷。
{"title":"Dearomative Addition of Carboranyl Anions to Isoquinolinium Salts and Subsequent Reduction to Access Carborane‐Functionalized Dihydroisoquinolines","authors":"Yun-Fan Gao, Chen-Ming Xu, Ming-Hui Yu, Yongna Zhang, Xiao-Jun Wu, You-Qing Wang","doi":"10.1002/ajoc.202400390","DOIUrl":"https://doi.org/10.1002/ajoc.202400390","url":null,"abstract":"A dearomative addition of readily available carboranyllithium reagents to isoquinolinium salts gave a series of carborane cage C‐substituted 1,2‐dihydroisoquinolines in 43−85% yields. Subsequent hydrogenation enabled the facile synthesis of corresponding carboranyl 1,2,3,4‐tetrahydroisoquinolines in 65−95% yields. The addition‐reduction pathway is applicable to a wide range of substituted isoquinolinium salts and o‐carborane or m‐carborane.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217007","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}
The synthesis of polycyclic compounds is highly valued due to the ubiquitous presence of these structures in pharmaceuticals and natural substances. Cycloaddition reactions are notable as one of the most important reaction classes in chemical synthesis due to their ability to generate polycyclic compounds in a single step using straightforward and easily accessible starting materials. In recent times, visible‐light‐mediated photocatalysis has emerged as a powerful tool for enabling a wide range of transformations. Significant advancements have been achieved in dearomative cycloaddition reactions induced by visible light over the past several years. This review offers an overview of visible‐light‐induced dearomative cycloaddition reactions categorized according to the method of substrate excitation ‐ a) Visible light induced dearomative photocatalytic cycloaddition by Energy Transfer (Ent); b) Visible light induced dearomative cycloaddition by direct excitation, c) Visible light induced dearomative radical cyclization.
{"title":"catalytic Dearomative Cycloaddition Reactions enabled by visible light","authors":"DEBAJYOTI SAHA","doi":"10.1002/ajoc.202400374","DOIUrl":"https://doi.org/10.1002/ajoc.202400374","url":null,"abstract":"The synthesis of polycyclic compounds is highly valued due to the ubiquitous presence of these structures in pharmaceuticals and natural substances. Cycloaddition reactions are notable as one of the most important reaction classes in chemical synthesis due to their ability to generate polycyclic compounds in a single step using straightforward and easily accessible starting materials. In recent times, visible‐light‐mediated photocatalysis has emerged as a powerful tool for enabling a wide range of transformations. Significant advancements have been achieved in dearomative cycloaddition reactions induced by visible light over the past several years. This review offers an overview of visible‐light‐induced dearomative cycloaddition reactions categorized according to the method of substrate excitation ‐ a) Visible light induced dearomative photocatalytic cycloaddition by Energy Transfer (Ent); b) Visible light induced dearomative cycloaddition by direct excitation, c) Visible light induced dearomative radical cyclization.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217009","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}
An efficient new method has been developed for the synthesis of ketone‐integrated cyclopentene‐fused indoline derivatives with a high regioselectivity through gold‐catalyzed oxidative cyclo‐coupling of 1,3‐enynes with indoles by using 2,6‐dichloropyridine N‐oxide as the terminal oxidant. A plausible mechanism has been proposed, in which, a cascade process of nucleophilic trapping of the vinyl gold carbene surrogate with indole followed by the subsequent intramolecular cyclization provides the dearomative formal [3+2] cycloaddition product. In addition, a scale‐up reaction and further derivation via cyclopentene’s epoxidation & hydrazone derivative’s 1,5‐ electrocyclization have been performed.
{"title":"Gold Catalyzed [3+2] Oxidative Annulation of 1,3‐Enyne with Indole","authors":"Zili Chen, Qiang Zou, Yu-Jiang Wang, Ya-Ru Wan","doi":"10.1002/ajoc.202400356","DOIUrl":"https://doi.org/10.1002/ajoc.202400356","url":null,"abstract":"An efficient new method has been developed for the synthesis of ketone‐integrated cyclopentene‐fused indoline derivatives with a high regioselectivity through gold‐catalyzed oxidative cyclo‐coupling of 1,3‐enynes with indoles by using 2,6‐dichloropyridine N‐oxide as the terminal oxidant. A plausible mechanism has been proposed, in which, a cascade process of nucleophilic trapping of the vinyl gold carbene surrogate with indole followed by the subsequent intramolecular cyclization provides the dearomative formal [3+2] cycloaddition product. In addition, a scale‐up reaction and further derivation via cyclopentene’s epoxidation & hydrazone derivative’s 1,5‐ electrocyclization have been performed.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217013","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}
Mara L. Polo, David A. Echeverri, Laureana Soria, Victoria A. Vaillard, Gregorio Meira, Santiago E. Vaillard, Luis A. Ríos, Diana Estenoz
This work investigates the functionalization of molecules with non‐activated internal double bonds via thiol‐ene coupling (TEC) reaction. A comprehensive study of the reaction between cysteamine hydrochloride (CAHC) and methyl oleate (MO) was carried out. A series of reactions were conducted under different operating conditions in order to assess their effect on conversion and selectivity. Different conditions were considered like the type of atmospheres and solvents, a portionwise addition of CAHC, reagents concentrations, and excess of CAHC. Maximum conversion and selectivity were reached under inert atmosphere, diluted conditions, ethanol as solvent, and the addition of CAHC at the beginning of the reaction with a molar ratio of CAHC/MO of 3/1. This provides an approach for analyzing more complex reaction systems..
{"title":"THIOL‐ENE COUPLING REACTION FOR FUNCTIONALIZATION OF NON‐ACTIVATED ALKENES: AN EXPERIMENTAL STUDY ON THE CHEMISTRY OF THE METHYL OLEATE AMINATION","authors":"Mara L. Polo, David A. Echeverri, Laureana Soria, Victoria A. Vaillard, Gregorio Meira, Santiago E. Vaillard, Luis A. Ríos, Diana Estenoz","doi":"10.1002/ajoc.202400334","DOIUrl":"https://doi.org/10.1002/ajoc.202400334","url":null,"abstract":"This work investigates the functionalization of molecules with non‐activated internal double bonds via thiol‐ene coupling (TEC) reaction. A comprehensive study of the reaction between cysteamine hydrochloride (CAHC) and methyl oleate (MO) was carried out. A series of reactions were conducted under different operating conditions in order to assess their effect on conversion and selectivity. Different conditions were considered like the type of atmospheres and solvents, a portionwise addition of CAHC, reagents concentrations, and excess of CAHC. Maximum conversion and selectivity were reached under inert atmosphere, diluted conditions, ethanol as solvent, and the addition of CAHC at the beginning of the reaction with a molar ratio of CAHC/MO of 3/1. This provides an approach for analyzing more complex reaction systems..","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217016","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}
Hongjun Zhu, Tongtong Deng, Shan Hu, Xianyu Ying, Hui Wang
A simple ortho‐acylation of 4‐phenylquinazoline by a Pd‐catalyzed oxidative C–H activation was developed, with moderate yields, in which no prefunctionalized methylarenes were used as acylation reagents. Moreover, this methodology tolerates a wide range of functional groups. Radical scavenging experiments indicate that the acylation involves a benzoyl radical pathway.
{"title":"Palladium Catalyzed Direct Ortho C‐H Acylation of 4‐Phenylquinoline using Methylarenes as Acylation Reagents","authors":"Hongjun Zhu, Tongtong Deng, Shan Hu, Xianyu Ying, Hui Wang","doi":"10.1002/ajoc.202400394","DOIUrl":"https://doi.org/10.1002/ajoc.202400394","url":null,"abstract":"A simple ortho‐acylation of 4‐phenylquinazoline by a Pd‐catalyzed oxidative C–H activation was developed, with moderate yields, in which no prefunctionalized methylarenes were used as acylation reagents. Moreover, this methodology tolerates a wide range of functional groups. Radical scavenging experiments indicate that the acylation involves a benzoyl radical pathway.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217010","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}
Isochroman is one of the powerful scaffolds which demonstrated various important biologically activities. Herein we represented the novel and versatile method for the synthesis of valuable isochroman spiropyrazolones of difunctional peroxides and pyrazolones via [1+5] annulation. This process represents a novel spiroisocchroman synthesis protocol and is featured by good functional group compatibility, mild conditions and readily available substrates.
{"title":"Base induced synthesis of isochroman spiropyrazolones via bifunctional peroxides","authors":"jiaxu feng, Xiangdi Wang, Yingying Wu","doi":"10.1002/ajoc.202400438","DOIUrl":"https://doi.org/10.1002/ajoc.202400438","url":null,"abstract":"Isochroman is one of the powerful scaffolds which demonstrated various important biologically activities. Herein we represented the novel and versatile method for the synthesis of valuable isochroman spiropyrazolones of difunctional peroxides and pyrazolones via [1+5] annulation. This process represents a novel spiroisocchroman synthesis protocol and is featured by good functional group compatibility, mild conditions and readily available substrates.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217011","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}
Owing to their unique properties, propargylic alcohols have been recognized as one of the most attractive synthons in the field of organic synthesis. Particularly, with the aid of auxiliary group, the α‐functionalized propargylic alcohols have been frequently involved in the organocatalytic enantioselective substitutions, conjugate additions, annulations and related reactions in recent years. Accordingly, the present review highlights recent advancements in the application of α‐functionalized propargylic alcohols in the field of asymmetric organocatalysis, which is organized according to the type of auxiliary group.
{"title":"Recent Advances in Organocatalytic Enantioselective Reactions of α‐Functionalized Propargylic Alcohols","authors":"Yan Xia, Meiwen Liu, Wenjun Li, Pengfei Li","doi":"10.1002/ajoc.202400377","DOIUrl":"https://doi.org/10.1002/ajoc.202400377","url":null,"abstract":"Owing to their unique properties, propargylic alcohols have been recognized as one of the most attractive synthons in the field of organic synthesis. Particularly, with the aid of auxiliary group, the α‐functionalized propargylic alcohols have been frequently involved in the organocatalytic enantioselective substitutions, conjugate additions, annulations and related reactions in recent years. Accordingly, the present review highlights recent advancements in the application of α‐functionalized propargylic alcohols in the field of asymmetric organocatalysis, which is organized according to the type of auxiliary group.","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217012","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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