应用化学 ›› 2015, Vol. 32 ›› Issue (6): 641-646.DOI: 10.11944/j.issn.1000-0518.2015.06.140332

• 研究论文 • 上一篇    下一篇

左旋薄荷醇的不对称合成

王林a*(),李焕勇a,谭微a,王三永b,李春荣b,杨定乔c   

  1. a暨南大学分析测试中心 广州 510632
    b
    广东省食品工业研究所 广州 510308
    c华南师范大学化学与环境学院 广州 510006
  • 收稿日期:2014-09-25 接受日期:2015-01-13 出版日期:2015-06-10 发布日期:2015-06-10
  • 通讯作者: 王林
  • 基金资助:
    广东省教育部产学研结合项目(2011A090200039)广东省自然科学基金重点项目(S2013020013091)资助

Asymmetric Synthesis of L-menthol

WANG Lina, *, LI Huanyonga, TAN Weia, WANG Sanyongb, LI Chunrongb, YANG Dingqiaoc   

  1. aAnalytical and Testing Center,Ji'nan University,Guangzhou 510632,China
    bGuangdong Food Industry Institute,Guangzhou 510308,China
    cSchool of Chemistry and Environment,South China Normal University,Guangzhou 510006,China
  • Received:2014-09-25 Accepted:2015-01-13 Published:2015-06-10 Online:2015-06-10
  • Contact: Lin WANG
  • Supported by:
    Supported by the Industry-Academia Cooperation Project of the Ministry of Education of Guangdong Province(No.2011A090200039), the Natural Science Foundation of Guangdong Province(No.S2013020013091)

摘要:

以4-羟基-2-丁酮和异丙叉丙酮为起始原料,经羟醛缩合、不对称氢化、羰基还原、钌催化氢化等4步反应制得左旋薄荷醇。总产率为33%,非对映体过量de值达到93%。详细探讨了铜催化剂及其用量、手性配体的选择、反应溶剂和时间等因素对胡薄荷烯酮不对称氢化反应的影响。中间体及目标化合物均通过了1H NMR、13C NMR和HRMS等技术手段的分析测定及结构表征。

 

关键词: 左旋薄荷醇, 不对称氢化, 对映选择性, 手性配体

Abstract:

L-menthol was synthesized from the starting materials of 4-hydroxy-2-butanone and mesityl oxide in four steps consisting of aldol condensation, asymmetric hydrogenation, reduction of carbonyl group, and ruthenium catalyzed hydrogenation. The total yield is 33% and the diastereomeric excess is 93%. Furthermore, the effects of copper catalysts and their loading, chiral ligands, reaction time and solvents on the asymmetric hydrogenation of piperitenone were discussed in details. The intermediates and target compound were identified and characterized by 1H NMR, 13C NMR and HRMS.

Key words: L-menthol, asymmetric hydrogenation, enantioselectivity, chiral ligand

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