手性双哌啶衍生物用于甲基三氧化铼催化烯烃不对称环氧化反应  

Application of Chiral Bispidine Derivatives on the Asymmetric Epoxidation of Olefins Catalyzed by MTO

作　　者：王芳[1] 张月成[1] 冉维津[1] 赵继全[1] 

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《分子催化》2010年第3期240-246,共7页Journal of Molecular Catalysis(China)

基　　金：国家自然基金青年科学基金(批准号20806020);国家自然科学基金(批准号20776035)

摘　　要：以N-烷基-4-哌啶酮为原料,制备了几个手性双哌啶衍生物配体.以尿素-过氧化氢复合物(UHP)为氧化剂,甲醇为溶剂,将这些配体用于甲基三氧化铼(MTO)催化的前手性烯烃的环氧化反应,考察了各种反应参数对催化剂催化性能的影响.结果表明,手性双哌啶衍生物的加入可降低MTO的催化活性,但可提高环氧化物的选择性;这些配体对前手性烯烃的环氧化反应有较低的手性诱导作用,对映体过量值(ee值)只有4%-11%.讨论了对映选择性低的原因.Several chiral bispidine derivatives were synthesized from N-alkyl-4-piperidone and used as ligands in the asymmetric epoxidation of prochiral olefins catalyzed by methyltrioxorhenium （MTO） with urea-hydrogen peroxide （UHP） as oxidant in methanol. The effects of reaction parameters on the performance of catalyst were studied. The results revealed the chiral bispidine derivatives can decrease the catalytic activity of MTO,but increase of the selectivity of the epoxides. Meantime,all the chiral compounds showed low chiral induction in the asymmetric epoxidation of prochiral olefins. The enantio excesses （ee） are only in the range of 4% to 11%. The reasons leading to the low ee were discussed.

关 键 词：手性双哌啶衍生物 甲基三氧化铼 烯烃 不对称环氧化 苯乙烯 

分 类 号：O643.32[理学—物理化学]