On the regiospecificity of vanadium bromoperoxidase

被引:92
作者
Martinez, JS [1 ]
Carroll, GL [1 ]
Tschirret-Guth, RA [1 ]
Altenhoff, G [1 ]
Little, RD [1 ]
Butler, A [1 ]
机构
[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
关键词
D O I
10.1021/ja004176c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Vanadium haloperoxidase enzymes catalyze the oxidation of halide ions by hydrogen peroxide, producing an oxidized intermediate, which can halogenate an organic substrate or react with a second equivalent of hydrogen peroxide to produce dioxygen. Haloperoxidases are thought to be involved in the biogenesis of halogenated natural products isolated from marine organisms, including indoles and terpenes, of which many are selectively oxidized or halogenated. Little has been shown concerning the ability of the marine haloperoxidases to catalyze regioselective reactions. Here we report the regiospecific bromoperoxidative oxidation of 1,3-di-tert-butylindole by V-BrPO from the marine algae Ascophyllum nodosum and Corallina officina[is, Both enzymes catalyze the regiospecific oxidation of 1,3-di-tert-butylindole in a reaction requiring both H2O2 and Br- as substrates, but which produce the unbrominated 1,3-di-tert-butyl-2-indolinone product exclusively, in near quantitative yield (i.e. one H2O2 consumed per product). By contrast, reactions with the controlled addition of aqueous bromine solution (HOBr = Br-2 = Br-3(-)) produce three monobromo and one dibromo-2-indolinone products, all of which differ from the V-BrPO-catalyzed product, Further, reactivities of 1,3-di-tert-butyl-2-indolinone with both aqueous bromine and V-BrPO differ significantly and shed light onto the possible nature of the oxidizing intermediate. This is the first example of a regiospecific bromination by a vanadium haloperoxidase and further extends their usefulness as catalysts.
引用
收藏
页码:3289 / 3294
页数:6
相关论文
共 26 条
  • [1] Asymmetric sulfoxidation catalyzed by a vanadium-containing bromoperoxidase
    Andersson, M
    Willetts, A
    Allenmark, S
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (24) : 8455 - 8458
  • [2] Asymmetric sulfoxidation catalyzed by a vanadium bromoperoxidase: Substrate requirements of the catalyst
    Andersson, MA
    Allenmark, SG
    [J]. TETRAHEDRON, 1998, 54 (50) : 15293 - 15304
  • [3] Preliminary X-ray analysis of a new crystal form of the vanadium-dependent bromoperoxidase from Corallina officinalis
    Brindley, AA
    Dalby, AR
    Isupov, MN
    Littlechild, JA
    [J]. ACTA CRYSTALLOGRAPHICA SECTION D-BIOLOGICAL CRYSTALLOGRAPHY, 1998, 54 : 454 - 457
  • [4] Vanadium haloperoxidases
    Butler, A
    [J]. CURRENT OPINION IN CHEMICAL BIOLOGY, 1998, 2 (02) : 279 - 285
  • [5] MARINE HALOPEROXIDASES
    BUTLER, A
    WALKER, JV
    [J]. CHEMICAL REVIEWS, 1993, 93 (05) : 1937 - 1944
  • [6] BUTLER A, 1996, MECH BIOHALOGENATION, P55
  • [7] BIOTRANSFORMATION OF ALKENES BY HALOPEROXIDASES - REGIOSPECIFIC BROMOHYDRIN FORMATION FROM CINNAMYL SUBSTRATES
    COUGHLIN, P
    ROBERTS, S
    RUSH, C
    WILLETTS, A
    [J]. BIOTECHNOLOGY LETTERS, 1993, 15 (09) : 907 - 912
  • [8] DEBOER E, 1988, J BIOL CHEM, V263, P12326
  • [9] EVERETT RR, 1990, J BIOL CHEM, V265, P15671
  • [10] EVERETT RR, 1990, J BIOL CHEM, V265, P4908