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机构地区:[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 [2]中国科学院研究生院,北京100039
出 处:《分子催化》2008年第5期408-412,共5页Journal of Molecular Catalysis(China)
基 金:国家自然科学基金项目(20473107,20673130,20773147)
摘 要:手性Pd(Ⅱ)/P-PHOS(S)催化的丙烯/CO交替聚酮通过还原合成了一类新型手性聚多元醇.考察了4种还原剂LiAlH4,NaBH4,BH3.THF和Pd/C加氢对该聚酮的还原作用,其中LiAlH4和NaBH4可将聚酮分子链中羰基完全还原,生成手性交替聚多元醇,BH3.THF只能部分还原聚酮羰基,而Pd/C加氢对聚酮没有还原作用.A kind of novel chiral polyalcohols were synthesized by reducing chiral polyketones, which were prepared by alternating copolymerization of propene with CO catalyzed by chiral Pd (Ⅱ)/P-PHOS (S) complex. In the reduction process, LiAlH4, NaBH4, BH3 THF, and Pd/C catalytic hydrogenation were applied as reducing agents, respectively. When LiAlH4 or NaBH4 were used as reductants, keto-carbonyls in polyketone molecule were completely reduced to alcoholic hydroxyls, generating a novel chiral alternating polyalcohol smoothly. In the presence of BH3 THF, both keto-carbonyls and alcoholic hydroxyls were detected in products due to the partially reduction of polyketones, However, Pd/C catalytic hydrogenation of ployketones gave no desired products.
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