Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (10): 3382-3389.DOI: 10.6023/cjoc202208021 Previous Articles     Next Articles


钯催化烯烃的不对称Aza-Wacker反应: 高效合成手性1,3-噁嗪烷-2-酮

杨新拓a, 陈品红a, 刘国生*()   

  1. a 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 沪港化学合成联合实验室 分子合成科学卓越创新中心 中国科学院大学 上海 200032
    b 华东师范大学 庄长恭研究所 上海 200062
  • 收稿日期:2022-08-16 修回日期:2022-10-09 发布日期:2022-11-02
  • 通讯作者: 刘国生
  • 基金资助:
    国家重点研发计划(2021YFA1500050); 国家自然科学基金(21971255); 国家自然科学基金(91956202); 国家自然科学基金(21790330); 国家自然科学基金(21821002); 中国科学院前沿科学重点研究计划(QYZDJSSW-SLH055); 中国科学院国际伙伴计划(121731KYSB20190016)

Asymmetric Palladium-Catalyzed Aza-Wacker Reaction of Alkenes: Efficient Synthesis of Chiral 1,3-Oxazinan-2-ones

Xintuo Yanga, Pinhong Chena, Guosheng Liu()   

  1. a State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032
    b Chang-Kung Chuang Institute, East China Normal University, Shanghai 200062
  • Received:2022-08-16 Revised:2022-10-09 Published:2022-11-02
  • Contact: Guosheng Liu
  • Supported by:
    National Key R&D Program of China(2021YFA1500050); National Natural Science Foundation of China(21971255); National Natural Science Foundation of China(91956202); National Natural Science Foundation of China(21790330); National Natural Science Foundation of China(21821002); Science and Technology Commission of Shanghai Municipality(19590750400); Science and Technology Commission of Shanghai Municipality(21520780100); Science and Technology Commission of Shanghai Municipality(17JC1401200); Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDJSSW-SLH055); International Partnership Program of Chinese Academy of Sciences(121731KYSB20190016)

A Pd-catalyzed asymmetric aza-Wacker-type reaction with N-Ts carbamate as the nucleophile has been developed, which employed a C-6 substituted pyridinyl-oxazoline as the chiral ligand and benzoquinone (BQ) as the oxidant. This reaction provides an efficient access to chiral 1,3-oxazinan-2-ones with good efficiency and excellent enantioselectivity. Mechanistic studies indicated that the reaction is initiated by an intramolecular asymmetric aminopalladation.

Key words: aza-Wacker, palladium catalysis, asymmetric aminopalladation, chiral 1,3-oxazinan-2-ones, chiral pyridinyl- oxazoline