催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (1): 65-69.DOI: 10.1016/S1872-2067(10)60161-1

• 研究论文 • 上一篇    下一篇

Pd(OAc)2/(S)-P-PHOS 催化的丙烯与 CO 交替共聚合成手性功能高分子

王来来, 贾小静, 万博   

  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:2010-06-30 修回日期:2010-09-17 出版日期:2011-01-13 发布日期:2014-05-22

Synthesis of Chiral Functionalized Polymers by Alternating Copolymerization of Propene and CO Using the Pd(OAc)2/(S)-P-PHOS Catalyst

WANG Lailai*, JIA Xiaojing, WAN Bo   

  1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
  • Received:2010-06-30 Revised:2010-09-17 Online:2011-01-13 Published:2014-05-22

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摘要： 以丙烯和 CO 为原料, Pd(OAc)2/(S)-P-PHOS 为手性催化剂, 在有机溶剂中, 经不对称交替共聚反应合成了手性功能高分子聚酮. 当过量的还原剂 LiAlH4 和 NaBH4 分别还原聚酮时, 手性聚醇产率达 90%; 当 NaBH4/羰基摩尔比分别为 0.5, 1 和 2, 紫外光谱 (200~400 nm) 检测证明, 手性聚酮中羰基的 29%, 71% 和 81% 分别被还原; 使用过量的还原剂 BH3•THF 时, 手性聚酮中羰基只能部分被还原. 手性聚醇的数均分子量比手性聚酮的低, 产物手性聚醇的摩尔旋光度随还原反应条件而变化.

关键词: 醋酸钯, 手性双膦配体, 丙烯, 一氧化碳, 手性聚酮, 还原剂, 手性聚醇

Abstract: Pd(OAc)2 (palladium acetate)/(S)-P-PHOS ((S)-2,2′,6,6′-tetramethoxy-4,4′-bis(diphenyl)phosphino)-3,3′-bipyridine) catalysis systems were applied to the alternating copolymerization of propene and CO in organic solvents to synthesize chiral polyketones. The diastereoselective reduction of a chiral polyketone using excess LiAlH4 (lithium aluminum hydride) and NaBH4 (sodium borohydride) as reducing agents gave a new class of optically active polyalcohol and the product yield was more than 90%. In the presence of various amounts of NaBH4 (NaBH4/carbonyl molar ratio of 0.5, 1, and 2), quantitative measurements of the intensity of the carbonyl absorbance at 200–400 nm in the UV (ultraviolet) spectrum showed a reduction of 29%, 71%, and 81%, respectively, for the carbonyl groups. The use of excess BH3·THF (borane tetrahydrofuran complex) as a reducing agent resulted in a partial reduction of the carbonyl groups of the chiral polyketone. The molecular weight of the product was lower than that of the chiral polyketone and the molar optical rotations of the product varied with the reductive conditions.

Key words: palladium acetate, chiral diphosphous ligand, propene, carbon monoxide, chiral polyketone, reducing agent, chiral polyalcohol