Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (6): 1573-1585.DOI: 10.6023/cjoc202201033 Previous Articles     Next Articles

ACCOUNT

铜催化的直接型插烯反应研究进展

李晖a,*(), 殷亮b,*()   

  1. a 运城学院应用化学系 山西运城 044000
    b 中国科学院上海有机化学研究所 中国科学院天然产物有机合成化学重点实验室 上海 200032
  • 收稿日期:2022-01-20 修回日期:2022-02-25 发布日期:2022-03-08
  • 通讯作者: 李晖, 殷亮
  • 基金资助:
    山西省回国留学人员科研基金(2020-141); 山西省重点研发计划(201903D121105); 国家自然科学基金(21871287); 国家自然科学基金(21922114); 上海市科委基金(20JC1417100); 上海市科委基金(21XD1424800)

Research Progress of Copper-Catalyzed Direct Vinylogous Reactions

Hui Lia(), Liang Yinb()   

  1. a Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000
    b CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2022-01-20 Revised:2022-02-25 Published:2022-03-08
  • Contact: Hui Li, Liang Yin
  • Supported by:
    Grants from the Shanxi Scholarship Council of China(2020-141); Key R & D Program of Shanxi Province(201903D121105); National Natural Science Foundation of China(21871287); National Natural Science Foundation of China(21922114); Science and Technology Commission of Shanghai Municipality(20JC1417100); Science and Technology Commission of Shanghai Municipality(21XD1424800)

Vinylogous reaction serves as an efficient tool to introduce a new functional group at the γ-position (or even more remote position) of the parent functional group. The produced highly functionalized structure motifs (especially chiral ones) are ubiquitous in natural products, biologically active compounds and pharmaceuticals. Moreover, they work as important synthetic intermediates in organic syntheses. Therefore, asymmetric vinylogous reaction has gained extensive attention in recent years. Our group is interested in the development of efficient direct vinylogous reactions by using copper catalysts with a focus on the catalytic asymmetric variants. Herein, the advances in our group in this field are reviewed. Both α,β-unsaturated and β,γ-unsaturated compounds (including esters, aldehydes, ketones, phosphonates, sulfones, and nitriles) are used as the vinylogous pronucleophiles. Aldehydes, ketones, imines, and molecular oxygen are employed as the electrophiles. This account is divided into three sections based on the varied electrophiles: asymmetric vinylogous aldol reaction, asymmetric vinylogous Mannich reaction and vinylogous aerobic oxidative hydroxylation. By using suitable copper catalysts, these reactions generally afforded the vinylogous products in good to excellent yields with good to excellent control of regio-, diastereo-, and enantioselectivities.

Key words: vinylogous reaction, copper catalysis, asymmetric catalysis, aldol reaction, Mannich reaction, oxidative hydroxylation