小分子伯胺催化异噁唑有氧还原开环反应

doi:10.1016/S1872-2067(14)60200-X

催化学报 ›› 2015, Vol. 36 ›› Issue (2): 204-208.DOI: 10.1016/S1872-2067(14)60200-X

小分子伯胺催化异噁唑有氧还原开环反应

赵忠奎, 李仁志, 李宇, 王桂茹

大连理工大学精细化工国家重点实验室, 化工学院催化化学与工程系, 辽宁大连116024

收稿日期:2014-06-25 修回日期:2014-07-18 出版日期:2015-01-21 发布日期:2015-01-21
通讯作者: 赵忠奎
基金资助:
教育部新世纪优秀人才支持计划(NCET-12-0079); 中央高校基本科研业务费专项资金(DUT12LK51).

Simple primary amine catalyzed aerobic reductive ring-cleavage of isoxazole motif

Zhongkui Zhao, Renzhi Li, Yu Li, Guiru Wang

State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2014-06-25 Revised:2014-07-18 Online:2015-01-21 Published:2015-01-21
Supported by:
This work was supported by the Chinese Ministry of Education via the Program for New Century Excellent Talents in University (NCET-12-0079) and the Fundamental Research Funds for the Central Universities (DUT12LK51).

摘要/Abstract

摘要：

有机催化是催化领域的前沿.在水介质中, 以水合肼作为还原剂研究了小分子有机胺催化3-甲基蒽醌-[1,2-c]-异噁唑有氧还原开环反应高效合成1-氨基-2-乙酰基蒽醌,详细考察了不同种类有机胺对异噁唑有氧还原开环反应的催化性能, 发现小分子有机伯胺具有很好的还原开环催化性能. 在1倍水合肼存在下室温反应3 h, 3-甲基蒽醌-[1,2-c]-异噁唑转化率和目标产物1-氨基-2-乙酰基蒽醌选择性均可达到97.2%. 产物的分子结构经氢核磁谱和质谱得以确证. 此外, 提出了小分子有机伯胺催化3-甲基蒽醌-[1,2-c]-异噁唑有氧还原开环反应合成1-氨基-2-乙酰基蒽醌的可能反应机理.

null

关键词: 有机催化, 小分子伯胺, 有氧还原开环, 1-氨基-2-乙酰基蒽醌, 绿色化学

Abstract:

A clean and highly efficient catalytic aerobic reductive ring-cleavage of 3-methylanthra[1,2-c]isoxazole-6,11-dione to 1-amino-2-acetylanthraquinone was performed using simple organic amines as organocatalysts and water as a green reaction medium. This method provides a new clean transformation of isoxazole-containing compounds to the corresponding ortho-amino ketones. The catalytic performance of various organic amines was carefully screened, and simple organic primary amines were found to be promising practical catalysts with outstanding catalytic performance. Isopropylamine as the organocatalyst gave 97.2% conversion of 3-methylanthra[1,2-c]isoxazole-6,11-dione, with 97.2% selectivity to 1-amino-2-acetylanthraquinone, in the presence of oxygen only, using 1 equiv. of hydrazine hydrate at room temperature for 3 h. A possible mechanism is also proposed.

Key words: Organocatalysis, Simple primary amine, Aerobic reductive ring cleavage, 1-Amino-2-acetyl anthraquinone, Green chemistry

赵忠奎, 李仁志, 李宇, 王桂茹. 小分子伯胺催化异噁唑有氧还原开环反应[J]. 催化学报, 2015, 36(2): 204-208.

Zhongkui Zhao, Renzhi Li, Yu Li, Guiru Wang. Simple primary amine catalyzed aerobic reductive ring-cleavage of isoxazole motif[J]. Chinese Journal of Catalysis, 2015, 36(2): 204-208.

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小分子伯胺催化异噁唑有氧还原开环反应

Simple primary amine catalyzed aerobic reductive ring-cleavage of isoxazole motif

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