单面及双面手性金属卟啉配合物的不对称催化羟化反应  

Asymmetric Benzylic Hydroxylation Catalyzed by Mono-andBis-Faced Bridged Chiral Porphyrins

作　　者：任奇志[1] 刘双艳[1] 王爱琴[1] 丁晓健[1] 

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《无机化学学报》2008年第9期1438-1443,共6页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No20471037);上海市自然科学基金(No03ZR14061)资助项目

摘　　要：将卟啉环一侧有手性空腔的单面桥联铁卟啉1b及卟啉环两侧均有手性联萘空腔的双面桥联铁卟啉2b作为催化剂,室温下以亚碘酰苯为氧源,对芳香饱和烃底物进行了催化不对称羟化反应。结果表明,双面桥联手性卟啉2b的对映选择性(e.e.值)为58%～79%,高于文献报导相应的催化性能。对于单面桥联手性卟啉1b,当体系中存在含氮轴向配体时,e.e.值及反应产率都有了很大提高。同时发现在催化体系中选用不同溶剂会对催化体系的e.e.值及反应产物中醇/酮比有明显的影响。1b and 2b with single and double chiral binaphthyl pockets have been used as asymmetric hydroxylation catalysts of benzylic C-H bonds. Both catalysts show quite different stoiehiometric and enantioseleetive properties. Bis-faced bridged 2b exhibits enantiomeric excesses（e.e.） 58%-79%, higher than ever reported catalytic systems. The corresponding mono-faced bridged lb gives good e.e. value in the presence of nitrogen base ligand. Meanwhile, the solvent effect of the catalytic system can have a strong influence on the e.e. value and alcohol/ketone ratio of the catalytic products.

关 键 词：手性金属卟啉 不对称羟化 对映选择性 含氮配体 

分 类 号：O614.811[理学—无机化学] O643.321[理学—化学]