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Chinese Journal of Organic Chemistry >

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

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

ARTICLES

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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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

Cite this article

Yunshu Liu , Guodong Zhao , Wenju Wu , Yunze Wang , Yanchao Yu , Jun You , Bo Liu . Study on Asymmetric Conjugate Cyanation of 3,5-Dimethyl-N-α,β-unsaturated Acylpyrazole Catalyzed by Magnesium-Bisoxazoline Complex[J]. Chinese Journal of Organic Chemistry, 2022 , 42(1) : 208 -217 . DOI: 10.6023/cjoc202107061

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