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2020 , Vol. 78 >Issue 8: 758 - 762

DOI: https://doi.org/10.6023/A20050191

研究通讯

三氟乙酸酐(TFAA)促进的Stieglitz重排反应制备苯胺

  • 罗潇 ,
  • 焦宁
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  • 北京大学药学院 天然药物及仿生药物国家重点实验室 北京 100191

收稿日期: 2020-05-28

  网络出版日期: 2020-07-10

基金资助

项目受国家自然科学基金（Nos.21632001 and 21772002）资助.

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From Hydroxylamines to Anilines via Trifluoroacetic Anhydride (TFAA) Assisted Stieglitz Rearrangement

  • Luo Xiao ,
  • Jiao Ning
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  • State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing 100191

Received date: 2020-05-28

  Online published: 2020-07-10

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21632001 and 21772002).

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摘要

本工作使用简单易得的三氟乙酸酐作为活化试剂，拓展了Stieglitz重排反应的底物适用范围，发展了一种通过C—C键断裂由苯乙基羟胺制备芳基伯胺的方法.该反应条件较为温和且对官能团具有较好的兼容性.机理研究表明，反应经历了活性三氟乙酸酯中间体的原位生成，并通过C—C和N—O键的断裂实现芳基迁移的过程.

关键词： C—C键断裂; Stieglitz重排反应; 羟胺; 苯胺; 芳基迁移

本文引用格式

罗潇 , 焦宁 . 三氟乙酸酐(TFAA)促进的Stieglitz重排反应制备苯胺[J]. 化学学报, 2020 , 78(8) : 758 -762 . DOI: 10.6023/A20050191

Abstract

Hydroxylamines have a wide range of biological properties and have been used as a useful synthon in organic synthesis. In the past decades, many transformations of hydroxylamines have been developed and widely applied. In contrast, one of the interesting reactions of hydroxylamines through C—C bond cleavage, named Stieglitz rearrangement, was less developed. Due to the poor leaving ability of the hydroxyl groups, the reported Stieglitz rearrangement reactions suffered from the harsh conditions and the very limited substrate scope with triarylmethyl hydroxylamine substrates. Since an interesting C—C bond cleavage is involved which will extend the synthetic application of hydroxylamine, the practical method under mild conditions with broad substrate scope for Stieglitz rearrangement is very desired. However, there are three potential problems which need to be addressed. First, the activator must selectively react with the hydroxyl group but not the N-nucleophile of the hydroxylamine substrates. Secondary, a suitable leaving group must be generated to weaken the N—O bond. In addition, the employed activator must be inactive to the formed imine intermediates and the subsequent amine products. Herein, we developed an efficient Stieglitz rearrangement reaction of hydroxylamines under mild conditions for the preparation of corresponding primary aryl amines. This chemistry using simple trifluoroacetic anhydride (TFAA) as an activator resolves the issues mentioned above and therefore provides a practical protocol for the further transformation and application of hydroxylamines. Mechanistic studies demonstrate that the in situ generation of an active trifluoroacetate leaving group derived the aryl migration process via both of the C—C and N—O bond cleavage. A general procedure for the TFAA assisted stieglitz rearrangement is as follows: BF3·Et2O (28.4 mg, 0.2 mmol), TFAA (46.2 mg, 0.22 mmol) were added to the solution of hydroxylamine (0.2 mmol) in 2 mL hexafluoroisopropanol (HFIP). The reaction mixture was stirred at room temperature for 1 h. After that, the reaction was quenched by 4 mL 2 mol/L NaOH (aq.) and extracted by the mixture of petroleum ether and ethyl acetate (1∶1, V∶V). The combined organic phase was concentrated, and purified by flash chromatography on a short silica gel to afford the desired product (eluent: petroleum ether/ethyl acetate).

Key words： C—C bond cleavage; Stieglitz rearrangement; hydroxylamine; aniline; aryl migration

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