Minisci-Type Alkylation of N-Heteroarenes by N-(Acyloxy)phthalimide Esters Mediated by a Hantzsch Ester And Blue LED Light,Advanced Synthesis & Catalysis

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Minisci-Type Alkylation of N-Heteroarenes by N-(Acyloxy)phthalimide Esters Mediated by a Hantzsch Ester And Blue LED Light
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2021-12-15 , DOI: 10.1002/adsc.202101195
Philip Chan ₁ , Jiacheng Li ₁ , Suan Tan ₁ , Sara Kyne ₁

Affiliation

A synthetic method that enables the Hantzsch ester-mediated Minisci-type C2-alkylation of quinolines, isoquinolines and pyridines by N-(acyloxy)phthalimide esters (NHPI) under blue LED (light emitting diode) light (456 nm) is described. Achieved under mild reaction conditions at room temperature, the metal-free synthetic protocol was shown to be applicable to primary, secondary and tertiary NHPIs to give the alkylated N-heterocyclic products in yields of 21–99%. On introducing a chiral phosphoric acid, an asymmetric version of the reaction was also realised and provided product enantiomeric excess (ee) values of 53–99%. The reaction mechanism was delineated to involve excitation of an electron-donor acceptor (EDA) complex, formed from weak electrostatic interactions between the Hantzsch ester and NHPI, which generates the posited radical species of the redox active ester that undergoes addition to the N-heterocycle.

中文翻译：

Hantzsch 酯和蓝光 LED 光介导的 N-(酰氧基) 邻苯二甲酰亚胺酯对 N-杂芳烃的 Minisci 型烷基化

描述了一种在蓝色 LED（发光二极管）光（456 nm）下通过N- （酰氧基）邻苯二甲酰亚胺酯（NHPI）对喹啉、异喹啉和吡啶进行 Hantzsch 酯介导的 Minisci 型 C2 烷基化的合成方法。在室温下温和的反应条件下，无金属合成方案被证明适用于一级、二级和三级 NHPI，以得到烷基化N-杂环产物的产率为 21–99%。在引入手性磷酸后，还实现了反应的不对称形式，并提供了 53-99% 的产物对映体过量 (ee) 值。反应机制被描述为涉及电子供体受体 (EDA) 复合物的激发，该复合物由 Hantzsch 酯和 NHPI 之间的弱静电相互作用形成，其产生氧化还原活性酯的假定自由基物质，该自由基物质经历加成到N-杂环.

更新日期：2021-12-15

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