Intramolecular α-Oxygenation of Amines via N-Heterocyclic Carbene-Catalyzed Domino Reaction of Aryl Aldehyde: Experiment and DFT Calculation,CCS Chemistry

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Intramolecular α-Oxygenation of Amines via N-Heterocyclic Carbene-Catalyzed Domino Reaction of Aryl Aldehyde: Experiment and DFT Calculation
CCS Chemistry ( IF 9.4 ) Pub Date : 2019-09-09 , DOI: 10.31635/ccschem.019.20190020
Xiang-Yu Chen ₁ , Chao-Shen Zhang ₂ , Liang Yi _{1,

3} , Zhong-Hua Gao ₁ , Zhi-Xiang Wang ₂ , Song Ye _{1,

2}

Affiliation

We have developed an N-heterocyclic carbene (NHC)-catalyzed domino reaction with aryl aldehyde through a simple acyl azolium intermediate using phenyliodine(III) diacetate (PIDA) as an oxidant. Controlled experiments and density functional theory calculations supported a domino two-stage mechanism from aldehyde/amine to an α-oxygenation product, including NHC-catalyzed oxidation of the aldehyde to carboxylic acid via acyl azolium intermediate, and further, an addition of carboxylate to iminium intermediate. Our study reveals a new model for the oxidation of Breslow intermediate via electrophilic attack of the hydroxyl group by PIDA.

中文翻译：

N-杂环卡宾催化的芳醛多米诺反应使胺分子内发生α-氧合反应：实验和DFT计算

我们已经开发了一种N-杂环卡宾（NHC）催化的多芳基醛与芳基醛的反应，该反应是通过简单的酰基偶氮中间体，使用二乙酸苯基碘（III）（PIDA）作为氧化剂。受控实验和密度泛函理论计算支持了从醛/胺到α-加氧产物的多米诺两阶段机理，包括NHC催化的经由酰基偶氮中间体将醛氧化为羧酸，以及将羧酸盐添加至亚胺基中间。我们的研究揭示了一种新的模型，用于通过PIDA对羟基进行亲电攻击来氧化Breslow中间体。

更新日期：2020-06-24

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