(R)-TTCA·K催化下环己酮与丙烯腈的加成反应

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (1): 149.

(R)-TTCA·K催化下环己酮与丙烯腈的加成反应

商艳梅, 王会萍, 王磊, 李叶芝, 黄化民

吉林大学化学学院, 长春 130023

收稿日期:2004-09-08 出版日期:2005-01-10 发布日期:2005-01-10
通讯作者: 李叶芝(1944年出生),女,教授,博士生导师,从事不对称有机合成研究.E-mail:lyz335@jlu.edu.cn E-mail:lyz335@jlu.edu.cn
基金资助:
国家自然科学基金(批准号:20172019)资助

Addition of Cyclohexanone with Acrylonitrile Catalyzed by (R)-TTCA·K

SHANG Yan-Mei, WANG Hui-Ping, WANG Lei, LI Ye-Zhi, HUANG Hua-Min

College of Chemistry, Jilin University, Changchun 130023, China

Received:2004-09-08 Online:2005-01-10 Published:2005-01-10

摘要/Abstract

关键词: (R)-TTCA·, K手性催化剂, (S)-(+)-2-环己酮基丙腈, (S)-(-)-2-环己酮基丙酸

Abstract: It is one of the most attractive types of asymmetric synthesis that chiral commpounts are generated under the influence of chiral catalysts. In recent years catalytic asymmetric Michael addition by chiral metal complexes has been recognized as an efficient method for obtaining asymmetric products. In this work we reported that using potassium thiazolidine -2-thione-4-carboxylate [(R)-TTCA·K] as the chiral catalyst, the addition reaction of cyclohexanone with acrylonitrile was carried out and optically active (S)-(+)-2-cyanoethyl cyclohexanone 1 ([α] 20 D=+2.8°, e.e. 19%) and hydrolysis product of 1, (S)-(-)-2-oxocyclohexanepropionic acid 2 ([α] 20 D=-2.95°, e.e. 19%), were obtained. Enantiomeric excess of compound 1 was determined by resolution of (R,S)-2-oxocyclohexanepropionic acid with (-)-quinine. Compounds 1 and 2 were easily racemized at a long time for laying aside and in the presence of dil H₂SO₄ or dil base. When (S)-(+)-2-cyanoethyl cyclohexanone reacts with ethylene glycol in the presence of toluene sulfonic acid as the catalyst the racemic 2-ethylendioxy cyclohexyl propionitrile was obtained. The mechanism of the reaction of cyclohexanone with acrylonitrile would be a complicated catalysis process.

Key words: Chiral catalyst (R)-TTCA·K, (S)-(+)-2-Cyanoethyl cyclohexanone, (S)-(-)-2-Oxocyclohexanepropionic acid

中图分类号:

O621
O643.3

TrendMD:

商艳梅, 王会萍, 王磊, 李叶芝, 黄化民. (R)-TTCA·K催化下环己酮与丙烯腈的加成反应. 高等学校化学学报, 2005, 26(1): 149.

SHANG Yan-Mei, WANG Hui-Ping, WANG Lei, LI Ye-Zhi, HUANG Hua-Min . Addition of Cyclohexanone with Acrylonitrile Catalyzed by (R)-TTCA·K. Chem. J. Chinese Universities, 2005, 26(1): 149.

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