高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (11): 1846.

• 研究论文 • 上一篇    下一篇

N-方酰麻黄碱配体的合成及催化前手性芳酮的不对称还原反应

吕守茂1,2, 周海兵1, 张骥1, 谢如刚3, 周忠远3, 陈新滋4   

  1. 1. 四川大学化学系, 成都 610064;
    2. 湖北咸宁师范高等专科学校化学系, 咸宁 437005;
    3. 香港理工大学应用生物与化学技术系, 香港;
    4. 台湾中兴大学化学系, 台中
  • 收稿日期:2000-11-17 出版日期:2001-11-24 发布日期:2001-11-24
  • 通讯作者: 谢如刚(1938年出生),男,教授,博士生导师,从事生物有机及有机合成化学研究.E-mail:schemorg@mail.sc.cnin-fo.net E-mail:schemorg@mail.sc.cnin.fo.net
  • 基金资助:

    国家自然科学基金(批准号:29632004)资助

Studies on the Synthesis of Squaric Acid Ephedrine and Their Application in Asymmetric Catalytic Borane Reduction of Prochiral Ketones

L� Shou-Mao1,2, ZHOU Hai-Bing1, ZHANG Ji1, XIE Ru-Gang3, ZHOU Zhong-Yuan3, CHAN Albert-S.C.4   

  1. 1. Department of Chemistry, Sichuan University, Chengdu 610064, China;
    2. Department of Chemistry, Xianning Teachers College, Xianning 437000, China;
    3. Department of Applied Biologyand Chemical Technology, The Hong Kong Polytechnic University, Hong Kong, China;
    4. Department of Chemistry, National Chung-Hsing University, Taichung, China
  • Received:2000-11-17 Online:2001-11-24 Published:2001-11-24

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被引次数

6

摘要： 方酸与醇反应生成方酸二酯,后者与天然麻黄碱反应得到N-方酰麻黄碱或N-方酰双麻黄碱.单N-方酰麻黄碱与脂肪胺及硫氢化钠等反应合成了C-3位含氮和含硫的系列配体.首次将这些方酰麻黄碱配体经原位制备手性唑硼烷催化前手性芳酮及二酮的不对称还原反应,得到化学产率和e.e.值分别为85%～98%和52.5%～87.4%的手性仲醇.新化合物的结构已用IR,1HNMR,MS和元素分析所证实,化合物4b的晶体结构用X射线衍射确认.

关键词: 方酰麻黄碱, 手性唑硼烷, 不对称催化, 芳酮的还原

Abstract: Seven squaric acid ester amides or squaric acid diamides have been conveniently prepared by the reaction of natural ephedrine and squaric acid diesters, in which the later can be sythesized by refluxing squaric acid in the corresponding alcohols. When squaric acid amide ester 4a reacted with alkyl amines or was treated with aqueous sodium hydrosulfide, the new ligands which contain nitrogen or sulfur atom at C3 of squaric acid were obtained. Five ligands were synthesized for the first time. The chiral oxazaborolidines formed in situ have been used in the enantioselective borane reduction of prochiral ketones and diketones to afford the alcohols in the range 85%-98% yields and 52.5%-87.4% enantiomeric excess respectively. All new ligand structures were comfirmed by IR,1H NMR, MSand elemental analysis, the crystal structure of compound 4b was lerrified by X-ray diffraction.

Key words: Squaric ephedrine amide, Chiral oxazaborolidines, Asymmetric catalysis, Reduction of aryl ketones

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