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.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
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
关键词
手性金属卟啉
不对称羟化
对映选择性
含氮配体
chiral metalloporphyrins
asymmetric hydroxylation
enantiomeric excesses
nitrogen base ligand
