化学学报 ›› 2013, Vol. 71 ›› Issue (09): 1239-1242.DOI: 10.6023/A13040394 上一篇    下一篇

研究通讯

双功能配体促进的钯催化不对称醚化和胺化反应

杜乐a,b, 曹鹏b, 廖建a,b   

  1. a 中国科学院成都有机化学研究所 成都 610041;
    b 中国科学院成都生物研究所 天然产物研究中心 成都610041
  • 收稿日期:2013-04-11 出版日期:2013-09-14 发布日期:2013-04-22
  • 通讯作者: 廖建,E-mail:jliao@cib.ac.cn E-mail:jliao@cib.ac.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 21272226, 21202160 and 21072186)资助.

Bifunctional Ligand Promoted Pd-Catalyzed Asymmetric Allylic Etherification/Amination

Du Lea,b, Cao Pengb, Liao Jiana,b   

  1. a Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041;
    b Natural Products Research Center, Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041
  • Received:2013-04-11 Online:2013-09-14 Published:2013-04-22
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21272226, 21202160 and 21072186).

研究双亚砜膦配体(BiSO-P)亚砜基团的Bronsted碱性在协同催化反应中的作用. 1H NMR研究表明双亚砜膦与醇和胺等质子试剂形成氢键; 并将此类配体应用于钯催化的不对称醚化和胺化反应, 最高获得99% ee. 研究发现氢键的存在能有效提高反应的ee值, 配体亚砜基团在反应过程中同时起着Lewis和Bronsted碱的作用.

关键词: 手性双亚砜膦配体, 双功能, 氢键, 钯催化, 烯丙基醚化和胺化

A serious of bissulfoxide-phosphine ligands are examined on the Bronsted basicity of sulfinyl moiety. The effect of secondary binding property of the ligand is demostrated in Pd-catalyzed asymmetric allylic etherification and amination (up to 99% ee). And the application scope of this methodology to hydrogen-donor nucleophiles is investigated.

Key words: chiral bissulfoxide-phosphine ligands, bifunctional, hydrogen bond, Pd-catalysis, allylic etherification and amination