Enamine Acylation Enabled Desymmetrization of Malonic Esters,Journal of the American Chemical Society

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Enamine Acylation Enabled Desymmetrization of Malonic Esters
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-12 , DOI: 10.1021/jacs.4c09276
Yu-Ping He _{1,

2} , Zhuo-Chen Li ₁ , Zi-Qi Wang ₁ , Wen-Ya Zheng ₁ , Hua Wu ₁

Affiliation

Asymmetric enamine alkylation represents a powerful tool for stereoselective C–C bond formation; in contrast, the development of enantioselective enamine acylation remains elusive. Here, we report that a chiral phosphoric acid can render an in-situ-formed enamine to undergo a stereoselective intramolecular α-carbon acylation, providing an alternative approach for the synthesis of useful pyrrolinones and indolinones bearing tetrasubstituted stereocenters. Utilizing an effective integration of the desymmetrization strategy and bifunctional organocatalysis, the first example of enantioselective enamine acylation is achieved by employing readily available aminomalonic esters and cyclic ketones. Instead of reactive and moisture-sensitive acyl chlorides, common esters with low electrophilicity were successfully used as efficient acylating reagents via hydrogen bonding interactions. The utility is demonstrated in the concise and enantioselective synthesis of (+)-LipidGreen I and II. Experimental studies and DFT calculations establish the reaction pathway and the origin of stereocontrol.

中文翻译：

烯胺酰化使丙二酸酯去对称化

不对称烯胺烷基化是立体选择性 C-C 键形成的有力工具；相比之下，对映选择性烯胺酰化的发展仍然难以捉摸。在这里，我们报道手性磷酸可以使原位形成的烯胺进行立体选择性分子内α-碳酰化，为合成带有四取代立构中心的有用吡咯啉酮和吲哚酮提供了另一种方法。利用去对称策略和双功能有机催化的有效整合，通过使用容易获得的氨基丙二酸酯和环酮实现了对映选择性烯胺酰化的第一个例子。通过氢键相互作用，低亲电性的普通酯取代了反应性和湿度敏感的酰氯，成功地用作有效的酰化试剂。 (+)-LipidGreen I 和 II 的简洁和对映选择性合成证明了该实用性。实验研究和 DFT 计算建立了反应途径和立体控制的起源。

更新日期：2024-09-12

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