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

被引：13

作者：

Chen, Xiang-Yu ^{[1
]}

Zhang, Chao-Shen ^{[2
]}

Yi, Liang ^{[1
,3
]}

Gao, Zhong-Hua ^{[1
]}

Wang, Zhi-Xiang ^{[2
]}

Ye, Song ^{[1
,2
]}

机构：

[1] Chinese Acad Sci, Inst Chem, CAS Res Educ Ctr Excellence Mol Sci, Beijing Natl Lab Mol Sci,CAS Key Lab Mol Recognit, Beijing 100190, Peoples R China

[2] Univ Chinese Acad Sci, Sch Chem Sci, Beijing 100049, Peoples R China

[3] Shandong Univ Weihai, Marine Coll, Weihai 264209, Peoples R China

来源：

CCS CHEMISTRY | 2019年 / 1卷 / 04期

基金：

中国国家自然科学基金;

关键词：

N-heterocyclic carbene; domino reactions; simple acyl azolium intermediates; alpha-oxygenation; DFT calculations;

D O I：

10.31635/ccschem.019.20190020

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 alpha-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. [GRAPHICS] .

引用

页码：343 / 351

页数：9

共 71 条

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