Cu(II)-nitroxyl radicals as catalytic galactose oxidase mimics

被引:189
作者
Dijksman, A [1 ]
Arends, IWCE [1 ]
Sheldon, RA [1 ]
机构
[1] Delft Univ Technol, Dept Biotechnol, Lab Biocatalysis & Organ Chem, NL-2628 BL Delft, Netherlands
关键词
D O I
10.1039/b305941c
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Results from Hammett correlation studies and primary kinetic isotope effects for the CuCl - TEMPO catalysed aerobic benzyl alcohol oxidations are inconsistent with an oxoammonium based mechanism. We postulate a copper-mediated dehydrogenation mechanism, in which TEMPO regenerates the active Cu(II)-species. This mechanism is analogous to that observed for Galactose Oxidase and mimics thereof.
引用
收藏
页码:3232 / 3237
页数:6
相关论文
共 43 条
  • [31] Copper-catalysed aerobic oxidation of alcohols using fluorous biphasic catalysis
    Ragagnin, G
    Betzemeier, B
    Quici, S
    Knochel, P
    [J]. TETRAHEDRON, 2002, 58 (20) : 3985 - 3991
  • [32] CHEMICAL-MODELS OF ENZYMATIC OXIDATION - OXIDATION OF PRIMARY ALCOHOLS IN ALKALINE MEDIA CATALYZED BY COPPER-COMPLEXES
    SAKHAROV, AM
    SKIBIDA, IP
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1988, 48 (2-3): : 157 - 174
  • [33] MECHANISM OF THE OXIDATION OF ALCOHOLS BY 2,2,6,6-TETRAMETHYLPIPERIDINE NITROSONIUM CATION
    SEMMELHACK, MF
    SCHMID, CR
    CORTES, DA
    [J]. TETRAHEDRON LETTERS, 1986, 27 (10) : 1119 - 1122
  • [34] OXIDATION OF ALCOHOLS TO ALDEHYDES WITH OXYGEN AND CUPRIC ION, MEDIATED BY NITROSONIUM ION
    SEMMELHACK, MF
    SCHMID, CR
    CORTES, DA
    CHOU, CS
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (11) : 3374 - 3376
  • [35] Sheldon R.A., 1981, METAL CATALYSED OXID
  • [36] New developments in catalytic alcohol oxidations for fine chemicals synthesis
    Sheldon, RA
    Arends, IWCE
    Dijksman, A
    [J]. CATALYSIS TODAY, 2000, 57 (1-2) : 157 - 166
  • [37] Green, catalytic oxidations of alcohols
    Sheldon, RA
    Arends, IWCE
    Ten Brink, GJ
    Dijksman, A
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (09) : 774 - 781
  • [38] Active site models for galactose oxidase containing two different phenol groups
    Taki, M
    Kumei, H
    Nagatomo, S
    Kitagawa, T
    Itoh, S
    Fukuzumi, S
    [J]. INORGANICA CHIMICA ACTA, 2000, 300 : 622 - 632
  • [39] Catalytic galactose oxidase models: Biomimetic Cu(II)-phenoxyl-radical reactivity
    Wang, YD
    DuBois, JL
    Hedman, B
    Hodgson, KO
    Stack, TDP
    [J]. SCIENCE, 1998, 279 (5350) : 537 - 540
  • [40] Galactose oxidase model complexes: Catalytic reactivities
    Wang, YD
    Stack, TDP
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (51) : 13097 - 13098