A density functional theory investigation on bis(diethylamino)cyclopropenylidene catalyzed synthesis of 1,4-bifunctional compounds,Journal of Physical Organic Chemistry

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A density functional theory investigation on bis(diethylamino)cyclopropenylidene catalyzed synthesis of 1,4-bifunctional compounds
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2021-05-18 , DOI: 10.1002/poc.4219
Abhijit Shyam ₁ , Amit Kumar Pradhan ₁ , Paritosh Mondal ₁

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Bis(amino)cyclopropenylidenes (BACs) are the newly discovered umpolung catalysts with potential applications in the synthesis of numerous important organic moieties. A plausible mechanism for bis(diethylamino)cyclopropenylidene (Et-BAC) catalysed synthesis of 1,4-diketones has been investigated using density functional theory (DFT). The proposed catalytic cycle initiates with the nucleophilic interaction of in situ generated Et-BAC with p-methoxybenzaldehyde to form a zwitterionic intermediate, which on proton transfer reaction gives Breslow intermediate. Breslow intermediate then favours 1,4-umpolung addition reaction with chalcone followed by another proton transfer to regenerate the Et-BAC along with enolic form of the product. Enolic form ultimately transforms into the desired keto form, 1-(4-methoxyphenyl)-2,4-diphenylbutane-1,4-dione via protonated and free DBU aided proton shift mechanism. DFT-derived reactivity parameters along with frontier molecular orbital (FMO) analysis have been successfully utilised to reveal the umpolung efficacy of Et-BAC. This DFT exploration is in good accordance with experimental findings and also offers a deeper insight into the Et-BAC catalysed organic transformations.

中文翻译：

双(二乙氨基)环亚丙烯基催化合成1,4-双功能化合物的密度泛函理论研究

双（氨基）环丙烯基（BAC）是新发现的umpolung催化剂，在许多重要有机部分的合成中具有潜在应用。已经使用密度泛函理论 (DFT) 研究了双 (二乙氨基) 环亚丙烯基 (Et-BAC) 催化合成 1,4-二酮的合理机制。所提出的催化循环始于原位生成的 Et-BAC 与p的亲核相互作用。-甲氧基苯甲醛形成两性离子中间体，通过质子转移反应得到 Breslow 中间体。Breslow 中间体随后有利于与查耳酮进行 1,4-umpolung 加成反应，然后进行另一次质子转移，以再生 Et-BAC 以及产物的烯醇形式。烯醇形式最终通过质子化和游离 DBU 辅助质子转移机制转化为所需的酮形式，1-(4-甲氧基苯基)-2,4-二苯基丁烷-1,4-二酮。DFT 衍生的反应性参数以及前沿分子轨道 (FMO) 分析已成功用于揭示 Et-BAC 的 umpolung 功效。这种 DFT 探索与实验结果非常一致，并且还提供了对 Et-BAC 催化的有机转化的更深入的了解。

更新日期：2021-05-18

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