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Active Iron-Oxo and Iron-Peroxo Species in Cytochromes P450 and Peroxidases; Oxo-Hydroxo Tautomerism with Water-Soluble Metalloporphyrins

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Book cover Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations

Part of the book series: Structure and Bonding ((STRUCTURE,volume 97))

Abstract

Heme-containing monooxygenases are able to catalyze two different classes of oxidation reactions. The first class includes oxygenation reactions (hydroxylation, epoxidation, N- or S-oxide formation, etc.) which are mediated by an electrophilic oxidative species. The second class is represented by the oxidative deformylation of aldhehydes and involves a nucleophilic oxidant as active intermediate. The reductive activation of molecular oxygen by cytochromes P450 generates a nucleophilic iron(III)-peroxo species which produces by protonation an electrophilic high-valent iron-oxo [formally an iron(V)oxo] responsible for electrophilic oxygen atom transfers. The nucleophilic properties of the iron(III)-peroxo intermediate in cytochrome P450 are due to the porphyrin ring acting as electron reservoir and also to the negative charge accumulated on the proximal cysteine during the initial reduction step of the catalytic cycle. The nature of the high-valent iron-oxo species generated in the catalytic cycle of heme-peroxidases will be also discussed. Among the different methods for studying the oxygenation reactions mediated by high-valent metal-oxo porphyrin complexes, the recent discovery of the “oxo-hydroxo tautomerism” provides a useful tool to investigate the mechanism of O-atom transfer reactions in aqueous media.

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References

  1. Nelson DR, Koymans L, Kamataki T, Stegeman JJ, Feyereisen R, Waxman DJ, Waterman MR, Gotoh O, Coon MJ, Estabrook RW, Gunsalus IC, Nebert DW (1996) Pharmacogenetics 6: 1

    Article  CAS  Google Scholar 

  2. Ortiz de Montellano PR (ed) (1996) Cytochrome P450: structure, mechanism and biochemistry. Plenum, New York

    Google Scholar 

  3. Ullrich V (1979) Topics in Current Chemistry 83: 67

    Article  CAS  Google Scholar 

  4. Taube H (1965) J Gen Physiol 49: 29

    Article  CAS  Google Scholar 

  5. Hayaishi O (ed) (1974) Molecular mechanism of oxygen activation. Academic Press, New York

    Google Scholar 

  6. Groves JT, Han YZ (1996) In: Ortiz de Montellano PR (ed) Cytochrome P450: structure, mechanism and biochemistry. Plenum, New York, chap 1, pp 3–48

    Google Scholar 

  7. Meunier B (1992) Chem Rev 92: 1411

    Article  CAS  Google Scholar 

  8. Mansuy D (1987) Pure Appl Chem 59: 759

    Article  CAS  Google Scholar 

  9. Ostovic D, Bruice TC (1992) Acc Chem Res 25: 314

    Article  CAS  Google Scholar 

  10. Dolphin D, Traylor TG, Xie LY (1997) Acc Chem Res 30: 259

    Article  Google Scholar 

  11. Vaz ADN, McGinnity DF, Coon MJ (1998) Proc Natl Acad Sci USA 95: 3555

    Article  CAS  Google Scholar 

  12. Meunier B (2000) Biomimetic oxidations mediated by metal complexes. Imperial College Press, London

    Google Scholar 

  13. Bernadou J, Meunier B (1998) Chem Commun 2167

    Google Scholar 

  14. Poulos TL, Finzel BC, Howard AJ (1986) Biochemistry 25: 5314

    Article  CAS  Google Scholar 

  15. Poulos TL, Finzel BC, Howard AJ (1987) J Mol Biol 195: 687

    Article  CAS  Google Scholar 

  16. Griffin BW, Peterson JA (1972) Biochemistry 11: 4740

    Article  CAS  Google Scholar 

  17. Atkins WA, Sligar SG (1990) Biochemistry 29: 1271

    Article  CAS  Google Scholar 

  18. Poulos TL, Cupp-Vickery J, Li H (1996) In: Ortiz de Montellano PR (ed) (1996) Cytochrome P450: structure, mechanism and biochemistry. Plenum, New York, chap 4, pp 125–150

    Google Scholar 

  19. Ravichandran KG, Boddupalli SS, Hasemann CA, Peterson JA, Deisenhofer J (1993) Science 261: 731

    Article  CAS  Google Scholar 

  20. Gleria KD, Nickerson DP, Hill HAO, Wong LL, Fülöp V (1998) J Am Chem Soc 120: 46

    Article  Google Scholar 

  21. Raag R, Poulos TL (1989) Biochemistry 28: 7586

    Article  CAS  Google Scholar 

  22. Hanson LK, Eaton WA, Sligar SG, Gunsalus IC, Gouterman M, Connell CR (1976) J Am Chem Soc 98: 2672

    Article  CAS  Google Scholar 

  23. Caron C, Mitschler A, Rivere G, Ricard L, Schappacher M, Weiss R (1979) J Am Chem Soc 101: 7401

    Article  CAS  Google Scholar 

  24. Ueno T, Kuosumi Y, Yoshizawa-Kumagaye K, Nakajima K, Ueyama N, Okamura TA, Nakamura A (1998) J Am Chem Soc 120: 12,264

    Article  CAS  Google Scholar 

  25. Egawa T, Ogura T, Makino R, Ishimura Y, Kitagawa T (1991) J Biol Chem 266: 10,246

    CAS  Google Scholar 

  26. MacDonald IDG, Sligar SG, Christian JF, Unno M, Champion PM (1999) J Am Chem Soc 121: 376

    Article  CAS  Google Scholar 

  27. El-Kasmi D, Tetreau C, Lavalette D, Momenteau M (1995) J Am Chem Soc 117: 6041

    Article  CAS  Google Scholar 

  28. Benson DE, Suslick KS, Sligar SG (1997) Biochemistry 36: 5104

    Article  CAS  Google Scholar 

  29. Vidakovic M, Sligar SG, Li H, Poulos TL (1998) Biochemistry 37: 9211

    Article  CAS  Google Scholar 

  30. Vaz ADN, Roberts ES, Coon MJ (1991) J Am Chem Soc 113: 5886

    Article  CAS  Google Scholar 

  31. Roberts ES, Vaz ADN, Coon MJ (1991) Proc Natl Acad Sci USA 88: 8963

    Article  CAS  Google Scholar 

  32. Caspi E, Arunachalam T, Nelson PA (1986) J Am Chem Soc 108: 1847

    Article  CAS  Google Scholar 

  33. (a)_Ortiz de Montellano PR (1996) In: Ortiz de Montellano PR (ed) (1996) Cytochrome P450: structure, mechanism and biochemistry. Plenum, New York, chap 8, pp 245–303

    Google Scholar 

  34. (b)_Graham-Lorenze S, Amarneh B, White RE, Peterson JA, Simpson ER (1995) Protein Science 4: 1065

    Article  Google Scholar 

  35. Moali C, Boucher JL, Sari MA, Stueher DJ, Mansuy D (1998) Biochemistry 37: 10,453

    Article  CAS  Google Scholar 

  36. Ortiz de Montellano PR (1998) Acc Chem Res 31: 543

    Article  Google Scholar 

  37. Gerber NC, Sligar SG (1992) J Am Chem Soc 114: 8742

    Article  CAS  Google Scholar 

  38. Raag R, Martinis SA, Sligar SG, Poulos TL (1991) Biochemistry 30: 11,420

    CAS  Google Scholar 

  39. Shaik S, Filatov M, Schröder D, Schwarz H (1998) Chem Eur J 4: 193

    Article  CAS  Google Scholar 

  40. Everse J, Everse KE, Grisham MB (eds) (1991) Peroxidases in chemistry and biology (2 volumes). CRC Press, Boca Raton

    Google Scholar 

  41. Atkinson JF, Ingold KU (1993) Biochemistry 32: 9209

    Article  CAS  Google Scholar 

  42. Toy PH, Newcomb M, Hollenberg PF (1998) J Am Chem Soc 120: 7719

    Article  CAS  Google Scholar 

  43. Groves JT, McClusky GA, White RE, Coon MJ (1978) Biochem Biophys Res Commun 81: 154

    Article  CAS  Google Scholar 

  44. Iyer KR, Jones JP, Darbyshire JF, Trager WF (1997) Biochemistry 36: 7136

    Article  CAS  Google Scholar 

  45. Manchester JI, Dinnocenzo JP, Higgins LA, Jones JP (1997) J Am Chem Soc 119: 5069

    Article  CAS  Google Scholar 

  46. Vaz ADN, McGinnity DF, Coon MJ (1998) Proc Natl Acad Sci USA 95: 3555

    Article  CAS  Google Scholar 

  47. Toy PH, Newcomb M, Coon MJ, Vaz ADN (1998) J Am Chem Soc 120: 9718

    Article  CAS  Google Scholar 

  48. Siegbahn PEM, Crabtree RC (1999) J Am Chem Soc 121: 117

    Article  CAS  Google Scholar 

  49. Linde C, Akermark B, Norrby PO, Svensson M (1999) J Am Chem Soc 121: 5083

    Article  CAS  Google Scholar 

  50. Sisemore MF, Selke M, Burstyn JN, Valentine JS (1997) Inorg Chem 36: 979

    Article  CAS  Google Scholar 

  51. Selke M, Valentine JS (1998) J Am Chem Soc 120: 2652

    Article  CAS  Google Scholar 

  52. Wertz DL, Sisemore MF, Selke M, Driscoll J, Valentine JS (1998) J Am Chem Soc 120: 5331

    Article  CAS  Google Scholar 

  53. Ozette K, Leduc P, Palacio M, Bartoli JF, Barkigia KM, Fajer J, Battioni P, Mansuy D (1997) J Am Chem Soc 119: 6442

    Article  CAS  Google Scholar 

  54. Gisdakis P, Antonczak S, Köstlmeier S, Herrmann WA, Rösch N (1998) Angew Chem Int Ed 37: 2211

    Article  CAS  Google Scholar 

  55. Chen K, Que L (1999) Angew Chem Int Ed 38: 2227

    Article  CAS  Google Scholar 

  56. Groves JT, Haushalter RC, Nakamura M, Nemo TE, Evans BJ (1981) J Am Chem Soc 103: 2884

    Article  CAS  Google Scholar 

  57. Meunier B, Robert A, Pratviel G, Bernadou J (2000) In: Kadish K, Smith K, Guilard R (eds) The porphyrin handbook. Academic Press, San Diego, vol 4, chap 31, pp 119–187

    Google Scholar 

  58. Mandon D, Weiss R, Jayaraj K, Gold A, Terner J, Bill E, Trautwein AX (1992) Inorg Chem 31: 4404

    Article  CAS  Google Scholar 

  59. Gadjhede M, Schuller DJ, Henriksen A, Smith AT, Poulos TL (1997) Nature Structural Biol 4: 1032

    Article  Google Scholar 

  60. Urano Y, Higuchi T, Hirobe M, Nagano T (1997) J Am Chem Soc 119: 12,008

    Article  CAS  Google Scholar 

  61. Robert A, Loock B, Momenteau M, Meunier B (1991) Inorg Chem 30: 706

    Article  CAS  Google Scholar 

  62. Collins TJ, Gordon-Wylie SW (1989) J Am Chem Soc 111: 4511

    Article  CAS  Google Scholar 

  63. Collins TJ (1994) Acc Chem Res 27: 279

    Article  CAS  Google Scholar 

  64. Bottomley LA, Neely FL (1997) Inorg Chem 37: 5435

    Article  Google Scholar 

  65. Du Bois J, Tomooka CS, Hason J, Carreira EM (1997) Acc Chem Res 30: 364

    Article  CAS  Google Scholar 

  66. Bortolini O, Meunier B (1983) JCS Chem Commun 1364

    Google Scholar 

  67. Bortolini O, Ricci M, Meunier B, Friant P, Ascone I, Goulon J (1986) Nouv J Chim 10: 39

    CAS  Google Scholar 

  68. Ayougou K, Bill E, Charnock JM, Garner CD, Mandon D, Trautwein AX, Weiss R, Winkler H (1995) Angew Chem Int Ed Engl 34: 343

    Article  CAS  Google Scholar 

  69. Groves JT, Lee J, Maria SS (1997) J Am Chem Soc 119: 6269

    Article  CAS  Google Scholar 

  70. Jin N, Groves JT (1999) J Am Chem Soc 121: 2923

    Article  CAS  Google Scholar 

  71. English AM, Tsaprailis G (1995) Adv Inorg Chem 43: 79

    Article  CAS  Google Scholar 

  72. Meunier B (2000) In: Meunier B (ed) Biomimetic oxidations catalyzed by transition metal complexes. Imperial College Press, London (in press)

    Google Scholar 

  73. Dawson JH (1988) Science 240: 433

    Article  CAS  Google Scholar 

  74. Penner-Hahn JE, Eble KS, McMurry TJ, Renner M, Balch AL, Groves JT, Dawson JH, Hodgson KO (1986) J Am Chem Soc 108: 7819

    Article  CAS  Google Scholar 

  75. Chang CS, Yamazaki I, Sinclair R, Khalid S, Powers L (1993) Biochemistry 32: 923

    Article  CAS  Google Scholar 

  76. Paeng KJ, Kincaid JR (1988) J Am Chem Soc 110: 7913

    Article  CAS  Google Scholar 

  77. Chuang WJ, Van Wart HE (1992) J Biol Chem 267: 13,293

    CAS  Google Scholar 

  78. Ozaki SI, Inada Y, Watanabe Y (1998) 120: 8020

    Google Scholar 

  79. Nakajima R, Yamazaki I (1987) J Biol Chem 262: 2576

    CAS  Google Scholar 

  80. Ator MA, David SK, Ortiz de Montellano PR (1987) J Biol Chem 262: 14,954

    CAS  Google Scholar 

  81. Chang YT, Veitch NC, Leow GH (1998) J Am Chem Soc 120: 5168

    Article  CAS  Google Scholar 

  82. Gajhede M, Schuller DJ, Henriksen A, Smith AT, Poulos TL (1997) Nat Struct Biol 4: 1032

    Article  CAS  Google Scholar 

  83. Klibanov AM, Berman Z, Alberti BN (1981) J Am Chem Soc 103: 6263

    Article  CAS  Google Scholar 

  84. Ortiz de Montellano PR, Choe YS, DePillis G, Catalano CE (1987) J Biol Chem 262: 11,641

    Google Scholar 

  85. Baciocchi E, Lanzalunga O, Malandrucco S (1996) J Am Chem Soc 118: 8973

    Article  CAS  Google Scholar 

  86. Griffin BW (1991) In: Everse J, Everse KE, Grisham MB (eds) Peroxidases in chemistry and biology, vol II. CRC Press, Boca Raton, pp 85–137

    Google Scholar 

  87. Blanke SR, Hager LP (1988) J Biol Chem 263: 18,739

    CAS  Google Scholar 

  88. Sundaramoorthy M, Terner J, Poulos TL (1995) Structure 3: 1367

    Article  CAS  Google Scholar 

  89. Sundaramoorthy M, Terner J, Poulos TL (1998) Chem & Biol 5: 461

    Article  CAS  Google Scholar 

  90. Egawa T, Miki H, Ogura T, Makino R, Ishimura Y, Kitagawa T (1992) FEBS Let 305: 206

    Article  CAS  Google Scholar 

  91. Wagenknecht HA, Woggon WD (1997) Chem & Biol 4: 367

    Article  CAS  Google Scholar 

  92. Geigert J, Lee TD, Dalietos DJ, Hirano DS, Neidleman SL (1986) Biochem Biophys Res Commun 136: 778

    Article  CAS  Google Scholar 

  93. Debrunner PG, Dexter AF, Schulz CE, Xia YM, Hager LP (1996) Proc Natl Acad Sci USA 93: 12,791

    Article  CAS  Google Scholar 

  94. Allain EJ, Hager LP, Deng L, Jacobsen EN (1993) 115: 4415

    Google Scholar 

  95. Dexter AF, Lakner FJ, Campbell RA, Hager LP (1995) 117: 6412

    Google Scholar 

  96. Colonna S, Gaggero N, Manfredi A, Casella L, Gullotti M, Carrea G, Pasta P (1990) Biochemistry 29: 10,465

    Article  CAS  Google Scholar 

  97. Colonna S, Gaggero N (1994) Phosph Sulf Silicon 95–96: 103

    Article  Google Scholar 

  98. Kobayashi S, Nakano M, Kimura T, Schaap AP (1987) Biochemistry 26: 5019

    Article  CAS  Google Scholar 

  99. Van Handel MJH, Primus JL, Teunis C, Boersma MG, Osman AM, Veeger C, Rietjens IMCM (1998) Inorg Chem Acta 275/276:98

    Article  Google Scholar 

  100. Meunier B, Guilmet E, De Carvalho ME, Poilblanc R (1985) J Am Chem Soc 106: 6668

    Article  Google Scholar 

  101. Robert A, Meunier B (1988) New J Chem 12: 885

    CAS  Google Scholar 

  102. Nam W, Valentine JS (1993) J Am Chem Soc 115: 1772

    Article  CAS  Google Scholar 

  103. The denomination “oxo-hydroxo tautomerism” which is reminiscent of the keto-enol tautomerism appears to be more precise than “redox tautomerism” that we initially proposed inFabiano AS, Robert A, Meunier B (1994) J Am Chem Soc 116: 937 [103]

    Google Scholar 

  104. Bernadou J, Fabiano AS, Robert A, Meunier B (1994) J Am Chem Soc 116: 937

    Google Scholar 

  105. Ingold KU, MacFaul PA (2000) In: Meunier B (ed) Biomimetic oxidations catalyzed by transition metals. Imperial College Press, London, chap 2 (in press)

    Google Scholar 

  106. Hashimoto S, Tatsuno Y, Kitagawa T (1986) Proc Natl Acad Sci USA 83: 2417

    Article  CAS  Google Scholar 

  107. Makino R, Uno T, Nishimura Y, Iizuka T, Tsuboi M, Ishimura Y (1986) J Biol Chem 261: 8376

    CAS  Google Scholar 

  108. Hashimoto S, Tatsuno Y, Kitagawa T (1987) J Am Chem Soc 109: 8096

    Article  CAS  Google Scholar 

  109. Groves JT, Stern MK (1987) J Am Chem Soc 109: 3812

    Article  CAS  Google Scholar 

  110. Groves JT, Stern MK (1988) J Am Chem Soc 110: 8628

    Article  CAS  Google Scholar 

  111. Balahura RJ, Sorokin A, Bernadou J, Meunier B (1997) Inorg Chem 36: 3488

    Article  CAS  Google Scholar 

  112. Lee KA, Nam W (1997) J Am Chem Soc 119: 1916

    Article  CAS  Google Scholar 

  113. Pitié M, Bernadou J, Meunier B (1995) J Am Chem Soc 117: 2935

    Article  Google Scholar 

  114. Song R, Sorokin A, Bernadou J, Meunier B (1997) J Org Chem 62: 673

    Article  CAS  Google Scholar 

  115. Yang SJ, Nam W (1998) Inorg Chem 37: 606

    Article  CAS  Google Scholar 

  116. Prince S, Körber F, Cooke PR, Lindsay Smith JR, Mazid MA (1993) Acta Cryst C49: 1158

    CAS  Google Scholar 

  117. Jeon S, Bruice TC (1992) Inorg Chem 31: 4843

    Article  CAS  Google Scholar 

  118. Nam W, Goh YM, Lee YJ, Lim MH, Kim C (1999) Inorg Chem 38: 3238

    Article  CAS  Google Scholar 

  119. Wietzerbin K, Müller JG, Jameton RA, Pratviel G, Bernadou J, Meunier B, Burrows CJ (1999) Inorg Chem 38: 4123

    Article  CAS  Google Scholar 

  120. Sorokin A, Meunier B (1998) Eur J Inorg Chem 1269

    Google Scholar 

  121. Balch AL, Chan YW, Cheng RJ, La Mar GN, Latos-Grazynski L, Renner MW (1984) J Am Chem Soc 106: 7779

    Article  CAS  Google Scholar 

  122. Groves JT, Gross Z, Stern MK (1994) Inorg Chem 33: 5065

    Article  CAS  Google Scholar 

  123. Kaaret TW, Zhang GH, Bruice TC (1991) J Am Chem Soc 113: 4652

    Article  CAS  Google Scholar 

  124. Rachlewicz K, Latos-Grazynski L (1996) Inorg Chem 35: 1136

    Article  CAS  Google Scholar 

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  1. Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077, Toulouse cedex 4, France

    Bernard Meunier & Jean Bernadou

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    Bernard Meunier

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Meunier, B., Bernadou, J. (2000). Active Iron-Oxo and Iron-Peroxo Species in Cytochromes P450 and Peroxidases; Oxo-Hydroxo Tautomerism with Water-Soluble Metalloporphyrins. In: Meunier, B. (eds) Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations. Structure and Bonding, vol 97. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-46592-8_1

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