化学学报 ›› 2001, Vol. 59 ›› Issue (4): 587-593. 上一篇    下一篇

研究论文

新型手性方酸衍生物的合成及催化前手性芳酮的不对称 还原反应

吕守茂;周海兵;谢如刚;周忠远;陈新滋;杨登贵   

  1. 四川大学化学系.成都(610064);香港理工大学手性技术开放实验室与应用生物 和化学科技系;台湾省中兴大学化学系
  • 发布日期:2001-04-15

Study on the synthesis of new chiral derivatives of squaric acid and their application in asymmetric catalytic borane reduction of prochiral aryl ketones

Lu Shoumao;Zhou Haibing;Xie Rugang;Zhou Zhongyuan;Chen Xinzi;Yang Denggui   

  1. Sichuan Univ, Dept Chem.Chengdu(610064)
  • Published:2001-04-15

方酸经酯化后与手性氨基醇反应,继而与脂肪胺、硫醇等作用,首次合成了11个新型手性方酰氨基醇配体。研究了它们经原位制成手性恶唑硼烷催化前手性芳酮的不对称还原的性能,得到手性仲醇的化学产率和e.e值分别为88%~98%和42%~81%。新化合物的结构经IR,1^HNMR,MS及元素分析证实,4b的绝对构型经X射线衍射确认。

关键词: 方酸, 酮, 还原, 氨基醇, 恶唑P, 硼烷类

Eleven new chiral squaric aicd amidoalcohols bave been synthesized by reaction of alkyl amines or thiols with 3-butoxy-[(1'S,2'R)-(2' hydroxy-1',2'-diphenylethyl) amino]-3-cyclobutene-1,2-dione, which is prepared by the reaction of (1R, 2S)-2-amino-1,2-diphenylalcohol with dibutyl squrate. The in situ formed chiral oxazaborolidines have been used in the enantioselective borane reduction of prochiral ketones to afford the alcohol products in a range 88%~98% yield and 42% ~81% enantiomeric excesses, respectively. All of the new compounds are confirmed by IR, 1^H NMR, MS and element analysis, in which compound 4b is also confirmed by X-ray analysis.

Key words: SQUARIC ACID, KETONE, REDUCTION, AMINO ALCOHOL, BORANES

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