Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalyst  

Highly Chemical and Regio-selective Catalytic Oxidation with a Novel Manganese Catalys

作　　者：刘斌 陈怡 余成志 沈征武 

机构地区：[1]Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Chinese Journal of Chemistry》2003年第7期833-838,共6页中国化学（英文版）

基　　金：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 [Mn2IVμ-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 epoxi-dation 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.The chemical selectivity of a novel active manganese compound [Mn2IVμ-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 epoxi-dation 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.

关 键 词：TACN catalytic oxidation maganese BENZALDEHYDE 

分 类 号：O643.3[理学—物理化学]