Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (12): 3761-3770.DOI: 10.6023/cjoc202405020 Previous Articles     Next Articles

ARTICLE

钯/膦配合物催化Morita-Baylis-Hillman碳酸酯与氮杂二烯的[4+4]环化反应

朱波, 杨杨, 刘淇尹, 杜玮*(), 陈应春*()   

  1. 四川大学华西药学院 成都 610041
  • 收稿日期:2024-05-15 修回日期:2024-06-21 发布日期:2024-07-25
  • 基金资助:
    国家自然科学基金(21971166)

Palladium/Phosphine Complex Catalyzed [4+4] Annulations of Morita-Baylis-Hillman Carbonates and 1-Azadienes

Bo Zhu, Yang Yang, Qiyin Liu, Wei Du*(), Yingchun Chen*()   

  1. West China School of Pharmacy, Sichuan University, Chengdu 610041
  • Received:2024-05-15 Revised:2024-06-21 Published:2024-07-25
  • Contact: *E-mail:ycchen@scu.edu.cn;duweiyb@scu.edu.cn
  • Supported by:
    National Natural Science Foundation of China(21971166)

A [4+4] annulation reaction for the construction of medium-sized N-heterocycles is reported. This process involves the generation of all-carbon 1,4-dipoles containing a π-allylpalladium complex from Morita-Baylis-Hillman (MBH) carbonates under the catalysis of Pd/Synphos, which then undergo Michael addition/N-allylic alkylation with 1-azadienes. A spectrum of eight-membered N-heterocycles featuring a trisubstituted exo-cyclic double bond is furnished efficiently with moderate to good E/Z selectivity and moderate atroposelectivity. In addition, moderate enantioselectivity can be realized by using a chiral ligand or with the assistant of a chiral quaternary ammonium salt.

Key words: palladium/phosphine complex, Morita-Baylis-Hillman carbonates, all-carbon 1,4-dipoles, [4+4] annulation, eight-membered N-heterocycles