一种可回收和重复使用配体的合成及其在AD反应中的应用

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (11): 2028.

一种可回收和重复使用配体的合成及其在AD反应中的应用

金瑛, 孙晓莉, 张生勇, 姚志军, 王巧峰

第四军医大学化学教研室, 西安710032

收稿日期:2003-09-27 出版日期:2004-11-24 发布日期:2004-11-24
基金资助:
国家自然科学基金(批准号:20272082)资助

Sythesis of a Kind of Recoverable and Reusable Ligand and Its Application in AD Reaction

JIN Ying, SUN Xiao-Li, ZHANG Sheng-Yong, YAO Zhi-Jun, WANG Qiao-Feng

The Teaching and Research Section of Chemistry, the 4th Military Medical University, Xi′an 710032, China

Received:2003-09-27 Online:2004-11-24 Published:2004-11-24

摘要/Abstract

摘要： 以3,6-二氯哒嗪为桥联基与奎宁及二氢奎宁在NaH和DMF中反应,生成物奎宁一侧在AIBN存在下与巯基乙醇反应,进而氧化成砜.生成的金鸡纳生物碱衍生物新配体1在AD反应中对6种烯烃的二羟化反应表现了很高的对映选择性(88%～99%e.e.)和化学产率(74%～91%).配体1可以回收和重复使用,在以肉桂酸乙酯为底物的AD反应中,重复使用4次,其催化活性和对映选择性保持不变.

关键词: 可回收配体, 不对称二羟化, 手性连二醇

Abstract: Dichoropyridazine was reacted with quinidyl and dihydroquinidyl in the presence of NaH in DMF to give compound 2. The side of quinidyl was reacted with 2-mercaptoethanol, then was oxidized to give ligand 1. Ligand 1 delivers excellent enantioselectivity as well as specific chemoselectivity in the asymmetric dihydroxylation(AD) of six olefins(88%—99% e.e). and 74%—91% isolated yields were obtained in AD reaction. Furthermore this ligand can be recovered and reused. Its enantioselectivity and chemoselectivity were unchangeable when it was reused for four times in AD reaction with cinnamic ethyl as the substrate.

Key words: Recoverable ligand, Asymmetric dihydroxylation, Chiral vicinal diol

中图分类号:

O621

TrendMD:

金瑛, 孙晓莉, 张生勇, 姚志军, 王巧峰. 一种可回收和重复使用配体的合成及其在AD反应中的应用. 高等学校化学学报, 2004, 25(11): 2028.

JIN Ying, SUN Xiao-Li, ZHANG Sheng-Yong, YAO Zhi-Jun, WANG Qiao-Feng . Sythesis of a Kind of Recoverable and Reusable Ligand and Its Application in AD Reaction. Chem. J. Chinese Universities, 2004, 25(11): 2028.