| 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- and Bis- Faced Bridged Chiral Porphyrins |
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| 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。 |
| 关键词: 手性金属卟啉 不对称羟化 对映选择性 含氮配体 |
| 基金项目: |
| Abstract: 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 stoichiometric and enantioselective properties. Bis-faced bridged 2b exhibits enantiomeric excesses(e.e.) 58%～79%, higher than ever reported catalytic systems. The corresponding mono-faced bridged 1b 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. |
| Keywords: chiral metalloporphyrins asymmetric hydroxylation enantiomeric excesses nitrogen base ligand |
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| 任奇志,刘双艳,王爱琴,丁晓健.单面及双面手性金属卟啉配合物的不对称催化羟化反应[J].无机化学学报,2008,24(9):1438-1443. |
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