Oxidation with the "H2O2-manganese(IV) complex carboxylic acid" reagent -: 1.: Oxidation of saturated hydrocarbons with peroxy acids and hydrogen peroxide

被引:61
作者
Shul'pin, GB
Lindsay-Smith, JR
机构
[1] Russian Acad Sci, NN Semenov Chem Phys Inst, Moscow 117977, Russia
[2] Univ York, Dept Chem, York YO1 5DD, N Yorkshire, England
关键词
activation of C-H bond; alkanes; metal complex catalysis; oxidation; oxygenation; peroxy acids; hydrogen peroxide; manganese complexes; retention of configuration; stereoselective reactions; hydrocarbons;
D O I
10.1007/BF02641538
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The complex [LMnIV(O)(3)(MnL)-L-IV](PF6)(2) (1), where L is 1,4,7-trimethyl-1,4,7-triazacyclononane, catalyzes a highly efficient stereoselective oxygenation of saturated hydrocarbons in the presence of H2O2. A carboxylic acid is an obligatory component of the reaction mixture, while acetonitrile or acetone can be used as solvent. The reaction occurs, forming alkyl hydroperoxide, ketone, and alcohol. Substitution at the tertiary cart,on atom proceeds more easily than that at the secondary carbon atom, whereas primary C-H bonds are rather inactive. Oxidation of alkanes and alcohols with peroxy acids catalyzed by complex 1 occurs with lower efficiency.
引用
收藏
页码:2379 / 2386
页数:8
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共 51 条
  • [1] Mechanism of acid-catalyzed epoxidation of alkenes with peroxy acids
    Bach, RD
    Canepa, C
    Winter, JE
    Blanchette, PE
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (15) : 5191 - 5197
  • [2] DIMERIC MN(III)-TETRAARYLPORPHYRINS AS CATALYSTS FOR H2O2-PROMOTED OLEFIN EPOXIDATION
    BANFI, S
    MONTANARI, F
    POZZI, G
    QUICI, S
    [J]. TETRAHEDRON, 1994, 50 (30) : 9025 - 9036
  • [3] Manganese-porphyrins and -azaporphyrins as catalysts in alkene epoxidations with peracetic acid .2. Kinetics and mechanism
    Banfi, S
    Cavazzini, M
    Coppa, F
    Barkanova, SV
    Kaliya, OL
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1997, (08): : 1577 - 1583
  • [4] Homogeneous oxidation of aromatics in nucleus with peracetic acid catalyzed by iron and manganese phthalocyanine complexes
    Barkanova, SV
    Derkacheva, VM
    Dolotova, OV
    Li, VD
    Negrimovsky, VM
    Kaliya, OL
    Lukyanets, EA
    [J]. TETRAHEDRON LETTERS, 1996, 37 (10) : 1637 - 1640
  • [5] On the distinction between radical chemistry and gif chemistry
    Barton, DHR
    Launay, F
    LeGloahec, VN
    Li, TS
    Smith, F
    [J]. TETRAHEDRON LETTERS, 1997, 38 (49) : 8491 - 8494
  • [6] THE PHOTOLYSIS OF HYDROGEN PEROXIDE AT HIGH LIGHT INTENSITIES
    BAXENDALE, JH
    WILSON, JA
    [J]. TRANSACTIONS OF THE FARADAY SOCIETY, 1957, 53 (03): : 344 - 356
  • [7] Bolm C, 1997, SYNLETT, P687
  • [8] Radical versus ''oxenoid'' oxygen insertion mechanism in the oxidation of alkanes and alcohols by aromatic peracids. New synthetic developments
    Bravo, A
    Bjorsvik, HR
    Fontana, F
    Minisci, F
    Serri, A
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (26) : 9409 - 9416
  • [9] Highly selective epoxidation of alkenes and styrenes with H2O2 and manganese complexes of the cyclic triamine 1,4,7-trimethyl-1,4,7-triazacyclononane
    DeVos, D
    Bein, T
    [J]. CHEMICAL COMMUNICATIONS, 1996, (08) : 917 - 918
  • [10] Highly selective epoxidation catalysts derived from intrazeolite trimethyltriazacyclononane-manganese complexes
    DeVos, DE
    Meinershagen, JL
    Bein, T
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1996, 35 (19): : 2211 - 2213