Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (6): 1642-1649.DOI: 10.6023/cjoc201901004 Previous Articles     Next Articles

Special Issue: 金属有机化学

Articles

手性双噁唑啉金属络合物催化N-α,β-不饱和酰基化合物与C,N-二芳基硝酮的不对称1,3-偶极环加成反应

李明龙, 曹茜娴, 由君, 喻艳超, 武文菊, 刘波   

  1. 哈尔滨理工大学化学与环境工程学院 绿色化工技术黑龙江省高校重点实验室 哈尔滨 150040
  • 收稿日期:2019-01-04 修回日期:2019-03-02 出版日期:2019-06-25 发布日期:2019-05-15
  • 通讯作者: 由君, 喻艳超 E-mail:youjunjun@126.com;yycyychao@163.com
  • 基金资助:

    黑龙江省自然科学基金(No.LH2019B010)、国家自然科学基金(No.21506043)资助项目.

Asymmetric 1,3-Dipolar Cycloaddition Reaction of C,N-Diarylnitrone with N-α,β-Unsaturated Acyl Compounds Catalyzed by Chiral Bisoxazoline Metal Complex

Li Minglong, Cao Xixian, You Jun, Yu Yanchao, Wu Wenju, Liu Bo   

  1. Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040
  • Received:2019-01-04 Revised:2019-03-02 Online:2019-06-25 Published:2019-05-15
  • Contact: 10.6023/cjoc201901004 E-mail:youjunjun@126.com;yycyychao@163.com
  • Supported by:

    Project supported by the Natural Science Foundation of Heilongjiang Province (No. LH2019B010), and the National Natural Science Foundation of China (No. 21506043).

Asymmetric cycloaddition reactions catalyzed by Inda-BOX 1 metal complex between two kinds of electron-withdrawing alkenes and C,N-diarylnitrone have been studied respectively. Results showed that the 4-substituted products were mainly obtained in both reactions under the best conditions. When N-acryloyl oxazolidinone was used as dipolarophile, the exo/endo selectivity of the reaction was 100/0, and the ee of the exo product was as high as 97%. When N-acryloyl-3,5-dimethyl pyrazole was used as dipolarophile, the selectivity of exo/endo was 0/100, and the ee of endo product was up to 98%. The relationship of the dipolarophile, the structure of nitrone and the selectivity of the reaction was discussed.

Key words: asymmetric catalysis, 1,3-dipolar cycloaddition reaction, chiral dioxazoline, N-α,β-unsaturated acyl compounds, C,N-diarylnitrone, enantioselectivity