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2022 , Vol. 42 >Issue 1: 208 - 217

DOI: https://doi.org/10.6023/cjoc202107061

研究论文

镁-双噁唑啉络合物催化3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应研究

  • 刘云姝 ,
  • 赵国栋 ,
  • 武文菊 ,
  • 王云泽 ,
  • 喻艳超 ,
  • 由君 ,
  • 刘波
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  • 哈尔滨理工大学材料科学与化学工程学院 黑龙江省绿色化工技术重点实验室 哈尔滨 150040

收稿日期: 2021-07-29

  修回日期: 2021-09-01

  网络出版日期: 2021-09-08

基金资助

国家自然科学基金(22008045); 黑龙江省普通本科高等学校青年创新人才培养计划(UNPYSCT-2020199)

收起

Study on Asymmetric Conjugate Cyanation of 3,5-Dimethyl-N-α,β-unsaturated Acylpyrazole Catalyzed by Magnesium-Bisoxazoline Complex

  • Yunshu Liu ,
  • Guodong Zhao ,
  • Wenju Wu ,
  • Yunze Wang ,
  • Yanchao Yu ,
  • Jun You ,
  • Bo Liu
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  • Key Laboratory of Green Chemical Engineering and Technology of Heilongjiang Province, School of Materials Science andChemical Engineering, Harbin University of Science and Technology, Harbin 150040
* Corresponding authors. E-mail: ;

Received date: 2021-07-29

  Revised date: 2021-09-01

  Online published: 2021-09-08

Supported by

Natural Science Foundation of China(22008045); University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2020199)

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摘要

报道了镁-双噁唑啉络合物体系催化的TMSCN与3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应. 考察了BOX配体结构、配体与金属比例、温度、溶剂等对反应的影响. 研究结果表明, 使用双苄基取代的双噁唑啉配体与二丁基镁(物质的量比为2∶1)在1,2-二氯乙烷中原位生成手性催化剂, 催化剂用量为10 mol%, 反应温度为–32 ℃, 不对称共轭氰化反应催化效果最佳. 将上述催化方法应用于一系列3,5-二甲基-N-α,β-酰基吡唑衍生物, 绝大部分以90%以上的产率和中等以上的对映选择性获得相应的目标产物.

关键词： 双噁唑啉; 三甲基氰硅烷; 3,5-二甲基-N-α,β-不饱和酰基吡唑; 不对称共轭氰化

本文引用格式

刘云姝 , 赵国栋 , 武文菊 , 王云泽 , 喻艳超 , 由君 , 刘波 . 镁-双噁唑啉络合物催化3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应研究[J]. 有机化学, 2022 , 42(1) : 208 -217 . DOI: 10.6023/cjoc202107061

Abstract

The asymmetric conjugate cyanation reaction of TMSCN with 3,5-dimethyl-N-α,β-unsaturated acylpyrazole catalyzed by magnesium-bisoxazoline complex was studied. The effects of BOX ligand structure, ligand to metal ratio, temperature, solvent, etc. on the reaction were investigated. The results showed that when bis-benzyl substituted bisoxazoline ligand and dibutylmagnesium (molar ratio 2∶1) were used to generate chiral catalyst in situ in 1,2-dichloroethane, the amount of catalyst was 10 mol%, and the reaction temperature was –32 ℃, and the catalytic effect of asymmetric conjugate cyanation reaction was the best. The catalytic method above was applied to the conjugate cyanation reaction of a series of 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole derivatives, most of the corresponding target products could be obtained with more than 90% yield and moderate to good enantioselectivities.

Key words： bisoxazoline; TMSCN; 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole; asymmetric conjugate cyanation

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