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有机化学
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有机化学 ›› 2009, Vol. 29 ›› Issue (12): 1992-1996. 上一篇    下一篇

研究简报

手性的H‘4-NOBIN衍生物在不对称加成和取代反应中的应用

杜云锋a；李新生*,a,b；徐东成a,b   

  1. (a浙江师范大学化学与生命科学学院 金华 321004) 
    (b浙江师范大学物理化学研究所 浙江省固体表面反应化学重点实验室 金华 321004)
  • 收稿日期:2008-11-18 修回日期:2009-04-02 发布日期:2009-07-07
  • 通讯作者: 李新生 E-mail:sky33@zjnu.cn
  • 基金资助:

    国家级.国家自然科学基金

Application of Chiral H’4-NOBIN Derivatives in Asymmetric Addition and Alkylation

Du, Yunfenga；Li, Xinsheng*,a,b；Xu, Dongcheng a,b   

  1. (a Department of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004)
     (b Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004)
  • Received:2008-11-18 Revised:2009-04-02 Published:2009-07-07

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以手性 H’4-NOBIN为原料合成了新型手性氨基酚2和N,P配体5, 并将化合物2应用于催化二乙基锌对醛的不对称加成反应, 产率达90%, 对映体过量最高为45.9% ee. 化合物5用于钯催化的1,3-二苯基-2-烯丙基乙酸酯的不对称烯丙基烷基化反应, 产率为89%, 对映体过量最高为81.6% ee. 结果表明氨基酚2手性诱导作用弱于未氢化的NOBIN, 但却高于其八氢衍生物, 而N,P配体5给出相反的结果.

关键词: H‘4-NOBIN, 氨基酚, 二乙基锌, N,P配体, 烯丙基烷基化

Two chiral ligands (aminol and aminophosphine) derivatived from (R)-H'4-NOBIN were prepared. Chiral amino phenol 2 was employed as a catalyst in the asymmetric addition reaction of diethylzinc to aldehydes with the yield up to 90% and enantiomeric excesses up to 45.9% ee. Chiral N,P ligand 5 was examined for the asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with up to 89% yield and up to 81.6% ee. The results showed the H'4-NOBIN derivatives provided weaker chiral inducement than the parent compound but better induction than H8-NOBIN derivatives, while the chiral N,P ligand 5 displayed opposite results.

Key words: H‘4-NOBIN, amino phenol, diethylzinc, N,P ligand, allylic alkylation