Stereoselective mechanochemical synthesis of thiomalonate Michael adducts via iminium catalysis by chiral primary amines

IF 2.2 4区 化学 Q2 CHEMISTRY, ORGANIC Beilstein Journal of Organic Chemistry Pub Date : 2024-09-12 DOI:10.3762/bjoc.20.198
Michał Błauciak, Dominika Andrzejczyk, Błażej Dziuk, Rafał Kowalczyk
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Abstract

The study presents a novel approach utilizing iminium salt activation and mild enolization of thioesters, offering an efficient and rapid synthesis of Michael adducts with promising stereoselectivity and marking a significant advancement in mechanocatalysis. The stereoselective addition of bisthiomalonates 14 to cyclic enones and 4-chlorobenzylideneacetone proceeds stereoselectively under iminium activation conditions secured by chiral primary amines, in contrast to oxo-esters as observed in dibenzyl malonate addition. Mild enolization of thioesters allows for the generation of Michael adducts with good yields and stereoselectivities. Reactions in a ball mill afford product formation with similar efficacy to solution-phase reactions but with slightly reduced enantioselectivity, yet they yield products in just one hour compared to 24 or even 168 hours in solution-based reactions. It is noteworthy that this represents one of the early reports on the application of iminium catalysis using first-generation chiral amines under mechanochemical conditions, along with the utilization of easily enolizable thioesters as nucleophiles in this transformation.

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Beilstein J. Org. Chem. 2024, 20, 2313–2322. doi:10.3762/bjoc.20.198

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手性伯胺通过亚氨基催化立体选择性机械化学合成硫代丙二酸迈克尔加合物
摘要 该研究提出了一种利用亚胺盐活化和硫代酯温和烯醇化的新方法,提供了一种具有良好立体选择性的迈克尔加合物的高效快速合成方法,标志着机械催化领域的重大进展。双硫代丙二酸盐 1–4 与环烯酮和 4-氯亚苄基丙酮的立体选择性加成是在手性伯胺确保的亚胺活化条件下进行的,与丙二酸二苄酯加成中观察到的氧化酯形成鲜明对比。硫代酯的温和烯醇化可以生成迈克尔加合物,并具有良好的产率和立体选择性。在球磨机中进行的反应可以生成与溶液相反应相似的产物,但对映体选择性略有降低,而且只需 1 小时就能生成产物,而溶液相反应则需要 24 甚至 168 小时。值得注意的是,这代表了在机械化学条件下使用第一代手性胺进行亚胺催化应用的早期报告之一,以及在这种转化中利用易烯醇化的硫代酯作为亲核体。Chem.2024, 20, 2313–2322. doi:10.3762/bjoc.20.198
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来源期刊
CiteScore
4.90
自引率
3.70%
发文量
167
审稿时长
1.4 months
期刊介绍: The Beilstein Journal of Organic Chemistry is an international, peer-reviewed, Open Access journal. It provides a unique platform for rapid publication without any charges (free for author and reader) – Platinum Open Access. The content is freely accessible 365 days a year to any user worldwide. Articles are available online immediately upon publication and are publicly archived in all major repositories. In addition, it provides a platform for publishing thematic issues (theme-based collections of articles) on topical issues in organic chemistry. The journal publishes high quality research and reviews in all areas of organic chemistry, including organic synthesis, organic reactions, natural product chemistry, structural investigations, supramolecular chemistry and chemical biology.
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