壳聚糖酯钌络合物催化苯乙酮的不对称氢转移反应
收稿日期: 2014-06-18
修回日期: 2014-07-30
网络出版日期: 2014-08-26
基金资助
河北省自然科学基金(No.B2011202087)资助项目.
Asymmetric Transfer Hydrogenation of Acetophenone Promoted by Chitosan Ester Ruthenium Complex
Received date: 2014-06-18
Revised date: 2014-07-30
Online published: 2014-08-26
Supported by
Project supported by the Natural Science Foundation of Hebei Province (No. B2011202087).
研究了硬脂酸壳聚糖酯(O-stearoyl chitosan, SCS)与[RuCl2(p-cymene)]2原位形成催化剂对以异丙醇、甲酸钠为氢源的苯乙酮不对称氢转移反应的催化性能, 考察了反应时间、温度、四氢呋喃用量等因素对催化反应的影响. 硬脂酸壳聚糖酯在异丙醇/四氢呋喃的溶液中以胶束形式存在, 平均胶束粒径213 nm. 以异丙醇为氢供体时, 产物1-苯乙醇ee值可达62.9%, 四氢呋喃的用量对催化活性影响较大. 当异丙醇与四氢呋喃体积比为1:1时催化活性随温度升高而升高, 100 ℃时催化反应的催化效率(TOF)值可达48.5 h-1; 以甲酸钠作氢源时, 反应的TOF值及1-苯乙醇的ee分别可达29.4 h-1及53.0%.
刘兵 , 周宏勇 , 李云庆 , 王家喜 . 壳聚糖酯钌络合物催化苯乙酮的不对称氢转移反应[J]. 有机化学, 2014 , 34(12) : 2554 -2558 . DOI: 10.6023/cjoc201406025
The catalytic properties of the catalyst generated in situ from the reaction of Ru(II) compounds with chitosan based ligands were evaluated in the asymmetric transfer hydrogenation of acetophenone using isopropanol or sodium formate as hydrogen source. The effects of reaction time, temperature and the dosage of THF on the performance of the catalyst were evaluated. The O-stearoyl chitosan (SCS) is in the form of micelles with the average size of 213 nm in i-PrOH/THF solution. Using i-PrOH as hydrogen source, the ee value of 1-phenylethanol is up to 62.9%. The dosage of THF strongly affected the catalytic activity. The catalytic activity (TOF) is up to 30.4 h-1 at the volume ratio of i-PrOH to THF being 1:1. The TOF increased with the increase of the temperature. At 100 ℃, the TOF is up to 48.5 h-1. While using HCOONa as the hydrogen source, the TOF and ee values of 1-phenylethanol are 29.4 h-1 and 53.0%, respectively.
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