{"title":"用于水介质中醇的脱水胺化反应的两性纳米组装†。","authors":"Waqar Ahmed and Pil Seok Chae","doi":"10.1039/D4NJ02943G","DOIUrl":null,"url":null,"abstract":"<p >Nano-assemblies such as surfactant micelles and vesicles are widely used in drug carriers, bioreactors, and gene delivery, but can also be used as catalytic systems for chemical transformations. In the current study, we introduce nano-assemblies formed by a novel sulfonate-based amphiphilic catalyst, designated <strong>Cat-2</strong>, which are responsive to acid catalyst (HBF<small><sub>4</sub></small>) and metal catalyst (Fe(BF<small><sub>4</sub></small>)<small><sub>2</sub></small>). When the amphiphilic assemblies of <strong>Cat-2</strong> were applied for dehydrative aminations of allylic or benzylic alcohols, we obtained the desired sulfonamide or carboxamide products with reasonable to good yields (58–92%). This methodology was also applied for gram-scale synthesis of the FDA-approved drug naftifine. <strong>Cat-2</strong> formed small micelles (∼20 nm) in water, which were transformed into large nano-assemblies (∼550 nm) upon the addition of HBF<small><sub>4</sub></small> and Fe(BF<small><sub>4</sub></small>)<small><sub>2</sub></small>. This morphological change mainly originates from the coordination of the sulfonate group to Fe<small><sup>2+</sup></small>. The resulting <strong>Cat-2</strong>-Fe<small><sup>2+</sup></small> assemblies contain amide groups at the hydrophilic–hydrophobic interfaces, which act as mediators for an effective proton transfer from HBF<small><sub>4</sub></small> in a bulk solution to the alcoholic substrate in the assembly interior. As a result, the protonated alcoholic substrate undergoes dehydration to initiate a catalytic cycle for the dehydrative amination reaction. The present methodology is favorable due to its facile and green setup, cost effectiveness, and use of easily accessible and non-toxic catalysts. In addition, the current study provides insight into the design of nano-assemblies for catalyzing organic transformations.</p>","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Amphiphilic nano-assembly for dehydrative amination reactions of alcohols in aqueous medium†\",\"authors\":\"Waqar Ahmed and Pil Seok Chae\",\"doi\":\"10.1039/D4NJ02943G\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Nano-assemblies such as surfactant micelles and vesicles are widely used in drug carriers, bioreactors, and gene delivery, but can also be used as catalytic systems for chemical transformations. In the current study, we introduce nano-assemblies formed by a novel sulfonate-based amphiphilic catalyst, designated <strong>Cat-2</strong>, which are responsive to acid catalyst (HBF<small><sub>4</sub></small>) and metal catalyst (Fe(BF<small><sub>4</sub></small>)<small><sub>2</sub></small>). When the amphiphilic assemblies of <strong>Cat-2</strong> were applied for dehydrative aminations of allylic or benzylic alcohols, we obtained the desired sulfonamide or carboxamide products with reasonable to good yields (58–92%). This methodology was also applied for gram-scale synthesis of the FDA-approved drug naftifine. <strong>Cat-2</strong> formed small micelles (∼20 nm) in water, which were transformed into large nano-assemblies (∼550 nm) upon the addition of HBF<small><sub>4</sub></small> and Fe(BF<small><sub>4</sub></small>)<small><sub>2</sub></small>. This morphological change mainly originates from the coordination of the sulfonate group to Fe<small><sup>2+</sup></small>. The resulting <strong>Cat-2</strong>-Fe<small><sup>2+</sup></small> assemblies contain amide groups at the hydrophilic–hydrophobic interfaces, which act as mediators for an effective proton transfer from HBF<small><sub>4</sub></small> in a bulk solution to the alcoholic substrate in the assembly interior. As a result, the protonated alcoholic substrate undergoes dehydration to initiate a catalytic cycle for the dehydrative amination reaction. The present methodology is favorable due to its facile and green setup, cost effectiveness, and use of easily accessible and non-toxic catalysts. In addition, the current study provides insight into the design of nano-assemblies for catalyzing organic transformations.</p>\",\"PeriodicalId\":95,\"journal\":{\"name\":\"New Journal of Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"New Journal of Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj02943g\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Journal of Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj02943g","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Amphiphilic nano-assembly for dehydrative amination reactions of alcohols in aqueous medium†
Nano-assemblies such as surfactant micelles and vesicles are widely used in drug carriers, bioreactors, and gene delivery, but can also be used as catalytic systems for chemical transformations. In the current study, we introduce nano-assemblies formed by a novel sulfonate-based amphiphilic catalyst, designated Cat-2, which are responsive to acid catalyst (HBF4) and metal catalyst (Fe(BF4)2). When the amphiphilic assemblies of Cat-2 were applied for dehydrative aminations of allylic or benzylic alcohols, we obtained the desired sulfonamide or carboxamide products with reasonable to good yields (58–92%). This methodology was also applied for gram-scale synthesis of the FDA-approved drug naftifine. Cat-2 formed small micelles (∼20 nm) in water, which were transformed into large nano-assemblies (∼550 nm) upon the addition of HBF4 and Fe(BF4)2. This morphological change mainly originates from the coordination of the sulfonate group to Fe2+. The resulting Cat-2-Fe2+ assemblies contain amide groups at the hydrophilic–hydrophobic interfaces, which act as mediators for an effective proton transfer from HBF4 in a bulk solution to the alcoholic substrate in the assembly interior. As a result, the protonated alcoholic substrate undergoes dehydration to initiate a catalytic cycle for the dehydrative amination reaction. The present methodology is favorable due to its facile and green setup, cost effectiveness, and use of easily accessible and non-toxic catalysts. In addition, the current study provides insight into the design of nano-assemblies for catalyzing organic transformations.