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℃,O21 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.
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 0.1 MPa）.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.
出处
《分子催化》
EI
CAS
CSCD
北大核心
2012年第1期19-25,共7页
Journal of Molecular Catalysis(China)
关键词
分子氧
氧化
镍催化
醇
C-H官能团化
molecular oxygen
oxidation/nickel catalysis
alcohol
C-H functionalization
