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有机化学
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有机化学 ›› 2010, Vol. 30 ›› Issue (11): 1754-1758. 上一篇    下一篇

研究简报

(－)-Sparteine辅助的邻位锂化反应对映选择性合成具有平面手性的非对称二茂铁胺

周智明*,1，袁浩1，Snieckus, Victor 2   

  1. (1北京理工大学化工与环境学院 北京 100081)
    (2 Department of Chemistry, Queen s University, Kingston ON KL7 3N6, Canada)
  • 收稿日期:2009-12-15 修回日期:2010-04-07 发布日期:2010-06-22
  • 通讯作者: 周智明 E-mail:zzm@bit.edu.cn
  • 基金资助:

    国家自然科学基金

Enantioselective Synthesis of Unsymmetrical Ferrocenenylamides with Planar Chirality by (－)-Sparteine Mediated Directed or-tho-Lithiation

Zhou Zhiming*,1 Yuan Hao1 Snieckus Victor2   

  1. (1 School of Chemical Engineering & the Environment, Beijing Institute of Technology, Beijing 100081)
    (2 Department of Chemistry, Queen s University, Kingston ON KL7 3N6, Canada)
  • Received:2009-12-15 Revised:2010-04-07 Published:2010-06-22

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以非对称的N-乙基-N-异丙基-二茂铁酰胺为底物, 利用(－)-sparteine辅助的邻位锂化反应制备具有平面手性的二茂铁衍生物, 得到了很高的产率和对映选择性. 并测定了1-(N-乙基-N-异丙基)酰胺-2-碘-二茂铁(10a)的晶体结构. 研究发现, 非对称的二茂铁底物有利于强化底物的手性环境, 进而提高反应的对映选择性.

关键词: (－)-Sparteine, 邻位锂化反应, 非对称二茂铁胺, 平面手性二茂铁, 晶体结构

The unsymmetrical ferrocene substrate, {[N-ethyl-N-(1-methylethyl)-amino]-carbonyl}-ferro- cene, was used in (－)-sparteine me-diated directed ortho-lithiation to prepare the planer chiral ferrocene ligands. High yields and enati-oselectivities were obtained. Increased enatioinductions were observed in research work by introducing the unsymmetrical N-ethyl-N-(1-methylethyl)-carboxamide group. Moreover, crystal structure of the compound 1-{[N-ethyl-N-(1-methylethyl)-amino]carbonyl}-2-iodo-ferrocene (10a), was detected by X-ray single-crystal diffraction. The absolute configuration was determined as R for the planar chirality.

Key words: (－)-sparteine, directed ortho-lithiation, unsymmetrical ferroceylamide, planer chirality, crystal structure