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Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalyst
引用本文:刘斌,陈怡,余成志,沈征武.Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalyst[J].中国化学,2003,21(7):833-838.
作者姓名:刘斌  陈怡  余成志  沈征武
作者单位:ShanghaiInstituteofOrganicChemistry,ChineseAcademyofSciences,Shanghai200032,China
基金项目:Project supported by the Chinese National Young Scientist Research Fund(No.29502015)and Wang Kuangcheng Scientific Award.
摘    要:The chemical selectivity of a novel active manganese compound Mn2^IVμ-O)3(TMTACN)2] (PF6)2 (1) in catalytic oxidation reactions depended on the structure of substrates and 1 was able to catalyze the oxidation of toluene into benzaldehyde and/or benzoic acid under very mild conditions. The following results were obtained: (1) The selectivity of the oxidation depended on the electronic density of double bonds. Reactivity was absent when strong electron-witherawing groups were conjugated with double bonds. (2) Allylic oxidation reactions mostly take place when double bond is present inside a ring system, whilst epoxiclarion reactions occur when the alkene moiety is part of linear chain. (3) In ring systems, the methylene group was more likely to be oxidized than the methyl group on ailylic position. As expected, the C--H bonds at the bridgeheads were unreactive.The secondary hydroxyl groups are more easily to be oxidized than the primary hydroxyl groups.

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Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalys
LIU,Bin CHEN,Yi YU,Cheng-Zhi SHEN,Zheng-Wu.Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalys[J].Chinese Journal of Chemistry,2003,21(7):833-838.
Authors:LIU  Bin CHEN  Yi YU  Cheng-Zhi SHEN  Zheng-Wu
Institution:LIU,Bin CHEN,Yi YU,Cheng-Zhi SHEN,Zheng-Wu Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China
Abstract:The chemical selectivity of a novel active manganese compound MnIV/2 μ‐O)3 (TMTACN)2](PF6)2 (1) in catalytic oxidation reactions depended on the structure of substrates and 1 was able to catalyze the oxidation of toluene into benzaldehyde and/or benzoic acid under very mild conditions. The following results were obtained; (1) The selectivity of the oxidation depended on the electronic density of double bonds. Reactivity was absent when strong electron‐witherawing groups were conjugated with double bonds. (2) Allylic oxidation reactions mostly take place when double bond is present inside a ring system, whilst epoxidation reactions occur when the alkene moiety is part of linear chain. (3) In ring systems, the methylene group was more likely to be oxidized than the methyl group on allylic position. As expected, the C—H bonds at the bridgeheads were unreactive. The secondary hydroxyl groups are more easily to be oxidized than the primary hydroxyl groups.
Keywords:TACN  catalytic oxidation  maganese  benzaldehyde
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