手性金属络合物催化C,N-二苯基硝酮立体选择性环加成反应研究  

Research of steroselective cycloaddition reactions of C,N-diphenylnitrones catalyzed by chiral metal complexes

作　　者：刘波[1] 由君[1] 

机构地区：[1]哈尔滨理工大学化学与环境工程学院,哈尔滨150080

出　　处：《黑龙江大学自然科学学报》2008年第6期774-779,共6页Journal of Natural Science of Heilongjiang University

基　　金：国家自然科学基金资助项目(20272011)

摘　　要：研究了双吃恶唑啉、酒石酸衍生物(TADDOLate)和L-氨基酸席夫碱等三类手性配体与金属的络合物对二苯基硝酮与缺电子烯烃或乙烯基乙醚环加成反应的催化性能。结果表明:三类手性配体组成的金属络合物对反应的速度和收率有较大的提高;双吃恶唑啉和TADDOLate的络合物使无选择性的硝酮与缺电子烯烃的环加成反应变成区域专一性反应,对映异构体选择性最高达到76%;氨基酸席夫碱络合物使硝酮与乙烯基乙醚的环加成反应的endo/exo取向发生逆转,并且选择性达到90%以上。The steroselective cycloaddition reactions of C, N - diphenylnitrones with electron - deficient alkenes and ethyl vinyl ether catalyzed by chiral metal complexes of bisoxazoline, TADDOLate and L - amino acids Schiff bases was researched. The research results shown that the chiral metal complexes used three kind of chiral ligands in- creased the reactions rate and yield rate largely, the reactions between nitrone and electron- deficient alkenes be- came stereospecificity in presence of bisoxazoline metal complexes or metal - TADDOLate, and the best enantiose- lectivity of the reactions was 76%. The exo/endo selectivity of the reaction between nitrone and ethyl vinyl ether was reversed by metal complexes of L - amino acids Schiff bases, the endo - adduct was more than 90% in the presence of Schiff bases complexes.

关 键 词：手性配体 双吃恶唑啉 TADDOLate 氨基酸席夫碱 环加成反应 立体选择性 

分 类 号：O621.3[理学—有机化学]