Harnessing Deep Eutectic Solvents for Regioselective Polar Additions to α, β Unsaturated Ketones and Aldehydes.

IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2024-11-18 DOI:10.1002/cssc.202402083
Andrew W J Platten, Iva Manasi, Mario Campana, Karen J Edler, Eva Hevia
{"title":"Harnessing Deep Eutectic Solvents for Regioselective Polar Additions to α, β Unsaturated Ketones and Aldehydes.","authors":"Andrew W J Platten, Iva Manasi, Mario Campana, Karen J Edler, Eva Hevia","doi":"10.1002/cssc.202402083","DOIUrl":null,"url":null,"abstract":"<p><p>Advancing the use of air-sensitive polar organometallic Grignard and organolithium reagents under more environmentally benign conditions, here we report the addition of these reagents to α,β-unsaturated ketones and aldehydes using the deep eutectic solvent (DES) choline chloride (ChCl): glycerol (Gly) (1 : 2), under air. Reactions occur at room temperature within seconds with excellent regioselective control. Furthering understanding of how these C-C bond forming processes take place in these reaction media, we have explored the surface concentration of the organic substrate (chalcone) in DES using interfacial tension and neutron reflectivity measurements, finding that chalcone is concentrated at the DES-hydrocarbon interface compared to the bulk concentration, although the interfacial chalcone concentration is still relatively low in this system. The influence of aggregation of the organometallic reagent in the organic solvent employed has also been evaluated, revealing the importance of achieving a balance between activation (via de-aggregation) and stability (to avoid its decomposition in the DES). This DES approach has been successfully extended to double additions to α,β-unsaturated esters and for one pot sequential 1,4 and 1,2 additions to ketones, providing a new entry point to a range of tertiary-alcohols, minimising the use of organic solvents and avoiding intermediate time-consuming purification steps.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402083"},"PeriodicalIF":7.5000,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemSusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cssc.202402083","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

Advancing the use of air-sensitive polar organometallic Grignard and organolithium reagents under more environmentally benign conditions, here we report the addition of these reagents to α,β-unsaturated ketones and aldehydes using the deep eutectic solvent (DES) choline chloride (ChCl): glycerol (Gly) (1 : 2), under air. Reactions occur at room temperature within seconds with excellent regioselective control. Furthering understanding of how these C-C bond forming processes take place in these reaction media, we have explored the surface concentration of the organic substrate (chalcone) in DES using interfacial tension and neutron reflectivity measurements, finding that chalcone is concentrated at the DES-hydrocarbon interface compared to the bulk concentration, although the interfacial chalcone concentration is still relatively low in this system. The influence of aggregation of the organometallic reagent in the organic solvent employed has also been evaluated, revealing the importance of achieving a balance between activation (via de-aggregation) and stability (to avoid its decomposition in the DES). This DES approach has been successfully extended to double additions to α,β-unsaturated esters and for one pot sequential 1,4 and 1,2 additions to ketones, providing a new entry point to a range of tertiary-alcohols, minimising the use of organic solvents and avoiding intermediate time-consuming purification steps.

利用深共晶溶剂对 α、β 不饱和酮和醛进行区域选择性极性加成。
为了在更环保的条件下推进对空气敏感的极性有机金属格氏试剂和有机锂试剂的使用,我们在此报告了在空气中使用氯化胆碱(ChCl):甘油(Gly)(1:2)的深静态溶剂(DES)将这些试剂加成到 a-b 不饱和酮和醛中的情况。反应在室温下数秒内完成,具有极佳的区域选择性控制。为了进一步了解这些 C-C 键形成过程是如何在这些反应介质中发生的,我们利用界面张力和中子反射率测量法探索了 DES 中有机底物(查尔酮)的表面浓度,发现与主体浓度相比,查尔酮集中在 DES-烃界面,尽管在该体系中界面查尔酮浓度仍然相对较低。此外,还评估了有机金属试剂在有机溶剂中聚集的影响,揭示了在活化(通过去聚集)和稳定性(避免其在 DES 中分解)之间实现平衡的重要性。这种 DES 方法已成功扩展到 a-b 型不饱和酯的双加成,以及酮的 1,4 和 1,2 一锅顺序加成,为一系列叔醇提供了新的切入点,最大限度地减少了有机溶剂的使用,并避免了中间耗时的纯化步骤。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
期刊介绍: ChemSusChem Impact Factor (2016): 7.226 Scope: Interdisciplinary journal Focuses on research at the interface of chemistry and sustainability Features the best research on sustainability and energy Areas Covered: Chemistry Materials Science Chemical Engineering Biotechnology
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信