有机化学 ›› 2012, Vol. 32 ›› Issue (07): 1284-1289.DOI: 10.6023/cjoc1112271 上一篇    下一篇

研究论文

氰化钠和醛及苦杏仁粗酶一锅法合成手性氰醇

郑祖彪, 姚璐璐, 李忠洲, 李新军, 邹新琢   

  1. 华东师范大学化学系 上海 200062
  • 收稿日期:2011-12-27 修回日期:2012-02-21 出版日期:2012-07-25 发布日期:2012-03-09
  • 通讯作者: 邹新琢 E-mail:xzzou@chem.ecnu.edu.cn

Direct use of NaCN and aldehydes in one-pot asymmetric synthesis of cyanohydrins by crude (R)-oxynitrilase

Zheng Zubiao, Yao Lulu, Li Zhongzhou, Li Xinjun, Zou Xinzhuo   

  1. Department of Chemistry, East China Normal University, Shanghai 200062
  • Received:2011-12-27 Revised:2012-02-21 Online:2012-07-25 Published:2012-03-09

直接使用固体氰化钠代替易挥发的HCN 为氰源,用来源于苦杏仁的(R)-醇腈酶粗酶催化和醛的反应,并加入足量的HAc 来抑制非酶促反应和手性氰醇产物的外消旋化,一锅法合成了手性氰醇。考察了酸,(R)-醇腈酶粗酶,水,氰化钠和反应温度等因素对反应的影响。大部分反应底物的产物的产率及ee 值都大于95%。该方法简单,安全,低成本、高对映选择性和收率,具有很好的应用价值。

关键词: 氰化钠, (R)-醇腈酶, 一锅法, 不对称合成, 醛, 手性氰醇

Solid sodium cyanide (NaCN) could be directly used to substitute volatile HCN as cyanide source in the one-pot asymmetric cyanohydrination of aldehydes catalyzed by crude (R)-oxynitrilase from almond with enough acetic acid to restrain the nonenzymatic reaction and racemization of chiral cyanohydrins. The effects of acid, crude (R)-oxynitrilase, volume ratio of water phase, NaCN and reaction temperature on the reaction were investigated. The yields and enantionmeric excess of most of products are higher than 95%. The proposed method has a high application value because of its simplicity, safety, and low cost as well as excellent enantioselectivities and yields.

Key words: NaCN, (R)-oxynitrilase, one-pot, asymmetric synthesis, aldehydes, cyanohydrin