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(200～400am)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.
Pd(OAc)2 (palladium acetate)/(S)-P-PHOS ((S)-2,2',6,6'-tetrainethoxy-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 di-astereoselective reduction of a chiral polyketone using excess LiAIH4 (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 (NaBHk/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.
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