催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (12): 1057-1061.

• 研究论文 • 上一篇    下一篇

手性二胺修饰的Ru-TPP/γ-Al2O3催化苄叉丙酮不对称加氢反应

明方永,王金波,付海燕,陈骏,陈华,李贤均   

  1. 四川大学化学学院有机金属络合催化研究所, 绿色化学与技术教育部重点实验室, 四川成都 610064
  • 收稿日期:2007-12-25 出版日期:2007-12-25 发布日期:2007-12-25

Asymmetric Hydrogenation of Benzalacetone Catalyzed by Chiral Diamine-Modified Ru-TPP/γ-Al2O3

MING Fangyong, WANG Jinbo, FU Haiyan, CHEN Jun, CHEN Hua*, LI Xianjun   

  1. Institute of Homogeneous Catalysis, Key Lab oratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China
  • Received:2007-12-25 Online:2007-12-25 Published:2007-12-25

PDF

850

被引次数

21

摘要： 在温和条件下制备了三苯基膦(TPP)作保护剂的负载钌催化剂Ru-TPP/γ-Al2O3, 以(1S,2S)-1,2-二苯基乙二胺, (S)-1,1-二(对甲氧苯基)-2-异丙基乙二胺, (8S,9S)-9-氨基(9-脱氧)二氢辛可尼定和(1S,2S)-环己二胺为手性修饰剂,考察了Ru-TPP/γ-Al2O3在苄叉丙酮不对称加氢反应中的催化性能. 结果表明,以(1S,2S)-1,2-二苯基乙二胺作为修饰剂时,催化剂具有较高的活性和选择性. 在有K2CO3存在的异丙醇和水的混合溶液中,在氢气压力4 MPa, 40 ℃和8 h的条件下,苄叉丙酮的转化率达到了99%, 对羰基加氢的选择性大于98%, 不饱和醇的光学纯度ee值为47%.

关键词: 苄叉丙酮, 负载钌催化剂, 手性二胺, 不对称加氢, 不饱和醇

Abstract: The enantioselective hydrogenation of benzalacetone was catalyzed by chiral diamine-modified Ru-TPP/γ-Al2O3(TPP=triphenylphosphine), and the effect of chiral diamines, such as (1S,2S)-DPEN ((1S,2S)-1,2-diphenyl-1,2-ethylenediamine), (S)-1,1-di(4-anisyl)-2-isopropyl-1,2-ethylenediamine, (8S,9S)-9-amino (9-deoxy) dihydrocinchonidine, and (1S,2S)-1,2-diaminocyclohexane on the hydrogenation was investigated. The results showed that (1S,2S)-DPEN could efficiently improve the hydrogenation activity and the selectivity for benzalacetone. Under the optimum reaction conditions of 40 ℃, H2 pressure of 4.0 MPa in K2CO3/i-PrOH+H2O solution, and (1S,2S)-DPEN as the chiral modifier, the conversion and the selectivity for the unsaturated alcohol reached 99% and 98%, respectively, and the ee value of the unsaturated alcohol was up to 47%.

Key words: benzalacetone, supported ruthenium catalyst, chiral diamine, asymmetric hydrogenation, unsaturated alcohol