| 郑小琦.乙酸镍吡啶配合物催化的分子氧氧化反应研究[J].分子催化,2012,(1):19-25 |
| 乙酸镍吡啶配合物催化的分子氧氧化反应研究 |
| Ni(OAc)2 /Pyridine Complex Catalytic Oxidation of Benzylic Compounds and Alcohols with Molecular Oxygen |
| 投稿时间：2011-11-17 修订日期：2012-02-27 |
| DOI： |
| 中文关键词: 分子氧,氧化,镍催化,醇,C-H官能团化 |
| 英文关键词:molecular oxygen/ oxidation/ nickel catalysis/ alcohol/ C-H functionalization |
| 基金项目: |
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| 中文摘要: |
| Ni(OAc)2结合吡啶和叔丁基过氧化氢(TBHP)实现了苄基C-H与苄基醇类化合物在温和条件下(80-90℃, O2 1 atm)的选择性催化分子氧氧化反应。研究了过氧化物添加剂，配体，溶剂和温度的影响，得到了优化的反应条件。在苄基C-H的氧化中显示了很高的酮/醇选择性。用ESR法进行了Ni（III）的检测，证实了反应机理。竞争实验说明羰基化合物的生成不是因为醇继续氧化。酮可被解释为过氧化氢中间体受金属催化分解的产物。 |
| 英文摘要: |
| Ni(OAc)2 combined with pyridine and tert-Butylhydroperoxide (TBHP) affords selective catalytic aerobic oxidations of benzylic C-Hs and alcohols under mild conditions (80-90℃, O2 1 atm). The effects of ligand, solvent, temperature and the nature of the peroxide additives were investigated to give an optimised oxidation protocol for these compounds. In the oxidation of the benzylic C-Hs, a high ketone/ alcohol selectivity were obtained. Ni(III) was detected by ESR, and the mechanism was verified. Competition experiments revealed that formation of the carbonyl compounds is not a result of further oxidation of the alcohols. It is suggested that ketone are a product of metal-catalysed decomposition of the hydroperoxide. |
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