催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (7): 1143-1148.DOI: 10.1016/S1872-2067(10)60253-7

• 研究快讯 • 上一篇    下一篇

苯乙烯不对称三羰化反应一步合成手性 2-氧代-3-苯基戊二酸二甲酯

王来来*, 张勤生, 崔玉明   

  1. 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000
  • 收稿日期:2011-03-25 修回日期:2011-05-28 出版日期:2011-07-18 发布日期:2014-11-28

One-Step Synthesis of Chiral Dimethyl 2-Oxo-3-phenyl-glutarate in the Asymmetric Triple-carbonylation of Styrene

WANG Lailai*, ZHANG Qinsheng, CUI Yuming   

  1. State Key Laboratory for Oxo Synthesis & Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
  • Received:2011-03-25 Revised:2011-05-28 Online:2011-07-18 Published:2014-11-28

PDF

844

被引次数

3

摘要： 以苯乙烯、甲醇和 CO 为反应物, 首次采用双膦配体 (S)-P-PHOS 和乙酰丙酮钯原位制备的手性络合物新催化体系, 以对苯醌作为氧化剂, 对甲苯磺酸作助催化剂, 在甲醇溶剂中进行不对称三羰化反应一步合成手性 2-氧代-3-苯基戊二酸二甲酯. 与现有文献结果相比, 三羰化反应所需 CO 压力明显降低, 条件较为温和.

关键词: 苯乙烯, 不对称三羰化, 手性, 2-氧代-3-苯基-戊二酸二甲酯, 乙酰丙酮钯, 双膦配体

Abstract: The in-situ preparation of the novel chiral catalyst precursor, which are composed of (S)-2,2',6,6'-tetramethoxy- 4,4'-bis(diphenylphosphine)-3,3'-bipyridine ((S)-P-PHOS) and palladium 2,4-pentanedionate, have been described. These complexes were found to be effective in the asymmetric triple-carbonylation of styrene, reaching up to [α]D20 = +27o (c, 0.28, CH2Cl2) for dimethyl 2-oxo-3-phenyl-glutarate using benzoquinone as oxidant, p-toluenesulfonic acid as co-catalyst, and methanol as solvent.

Key words: styrene, asymmetric triple-carbonylation, chiral, dimethyl 2-oxo-3-phenyl-glutarate, palladium 2,4-pentanedionate, dipyridlphosphines