Toluene Dioxygenase Reactions

[Toluene Dioxygenase] [Toluene] [Trichloroethylene] [BBD Main Menu]

These tables list many of the reactions catalyzed by the versatile enzyme toluene dioxygenase from P. putida F1, EC 1.14.12.11, and a literature or personal reference for each reaction. Many of the reactions in this page are based on a review article: Hudlicky T, Gonzalez D, Gibson DT (1999) "Enzymatic dihydroxylation of aromatics in enantioselective synthesis: expanding asymmetric methodology" Aldrichimica Acta 32(2): 35-62. [Reaction] links to a EAWAG-BBD reaction. "ND" means that the product of reaction is not determined. If there are any reactions we have missed, please let us know.

These 109 reactions are organized into 5 major groups by substrate type (number in each group or subgroup):

	A. Acts on monocyclic aromatics (69)
              Dioxygenation (60)
              Monooxygenation (5)
              Sulfoxidation (4)

	B. Acts on fused aromatics (3)

	C. Acts on linked aromatics (7)

	D. Acts on aliphatic olefins (18)
              Allylic methyl group monooxygenation (8)
              Monooxygenation with allylic rearrangement (1)
              Dioxygenation (9)

        E. Acts on miscellaneous substrates (12)
References

A. Acts on Monocyclic Aromatics
Dioxygenation
No. Reactions Refs
1. Toluene ----> Toluene-cis-1,2-dihydrodiol [Reaction] [1]
2. Benzene ----> cis-Dihydrobenzenediol [2]
3. Perdeuteriobenzene ----> Perdeuteriobenzene-cis-1,2-dideuterodiol [2]
4. Chlorobenzene ----> 3-Chloro-cis-1,2-dihydroxycyclohexa-3,5-diene [3]
5. Bromobenzene ----> 3-Bromo-cis-1,2-dihydroxycyclohexa-3,5-diene [3]
6. Deuterated bromobenzene ----> (Bromobenzene-d5)-cis-2,3-dideuterodiol [4]
7. 1-Fluoro-4-iodobenzene ----> 1-Fluoro-4-iodo-cis-2,3-dihydroxycyclohexa-4,6-diene [4]
8. 1-Bromo-4-iodobenzene ----> 1-Bromo-4-iodo-cis-2,3-dihydroxycyclohexa-4,6-diene [5]
9. 1-Bromo-2,3-difluorobenzene ----> 1-Bromo-5,6-difluoro-cis-2,3-dihydroxycyclohexa-4,6-diene [6]
10. 1,3-Dibromobenzene ----> 1,5-Dibromo-cis-2,3-dihydroxycyclohexa-4,6-diene [7]
11. Benzenenitrile ----> cis-(1S,2R)-1,2-Dihydroxy-3-cyanocyclohexa-3,5-diene [3]
12. Propoxybenzene ----> Propoxybenzene-cis-2,3-dihydrodiol [8]
13. 4-Fluorotoluene ----> 4-Fluoro-cis-2,3-dihydroxy-2,3-dihydrotoluene [5]
14. 4-Chlorotoluene ----> 4-Chloro-cis-2,3-dihydroxy-2,3-dihydrotoluene [9]
15. o-Iodotoluene ----> 3-Iodo-4-methyl-cis-1,2-dihydroxycyclohexa-3,5-diene [4]
16. p-Iodotoluene ----> 3-Iodo-6-methyl-cis-1,2-dihydroxycyclohexa-3,5-diene [4]
17. m-Bromobenzotrifluoride ----> 3-Trifluoromethyl-5-bromo-cis-1,2-dihydroxycyclohexa-3,5-diene [6]
18. m-Bromobenzotrifluoride ----> 3-Bromo-5-trifluoromethyl-cis-1,2-dihydroxycyclohexa-3,5-diene [6]
19. (2-bromoethyl)benzene ----> (5S,6R)-1-(2-Bromoethyl)-cis-5,6-dihydroxycyclohexa-1,3-diene [10]
20. (2-Azidoethyl)benzene ----> (5S,6R)-1-(2-Azidoethyl)-cis-5,6-dihydroxycyclohexa-1,3-diene [11]
21. Phenethyl alcohol ----> (5S,6R)-1-(2-Hydroxyethyl)-5,6-dihydroxycyclohexa-1,3-diene [11]
22. (2-Cyanoethyl)benzene ----> (5S,6R)-1-(2-Cyanoethyl)-5,6-dihydroxycyclohexa-1,3-diene [11]
23. (2-Thiocyanatoethyl)benzene ----> (5S,6R)-1-(Thiocyanatoethyl)-5,6-dihydroxycyclohexa- 1,3-diene [11]
24. (2-Isothiocyanatoethyl)benzene ----> (5S,6R)-1-(2-Isothiocyanatoethyl)-5,6-dihydroxycyclohexa-1,3-diene [11]
25. (2-Acetoxyethyl)benzene ----> (5S,6R)-1-(2-Acetoxyethyl)-5,6-dihydroxycyclohexa-1,3-diene [11]
26. 2-(2-Bromoethyl)bromobenzene ----> 1-Bormo-2-(2-bromoethyl)-cyclohexa-1,5-diene-3,4-diol [12]
27. 2-Chlorostyrene ----> (2-Chlorophenyl)-1,2-ethanediol [13]
28. 4-Chlorostyrene ----> (1R)-1-(4-Chlorophenyl)-1,2-ethanediol [13]
29. 3-Chlorostyrene ----> (1S)-1-(3-Chlorophenyl)-1,2-ethanediol [13]
30. Styrene ----> 3-Ethenyl-cis-1,2-dihydroxycyclohexa-3,5-diene [13]
31. 4-Chlorostyrene ----> cis-4-Chloro-1-vinylcyclohexa-4,6-diene-2,3-diol [13]
32. 3-Chlorostyrene ----> (2R,3S)-cis-5-Chloro-1-vinylcyclohexa-4,6-diene-2,3-diol [13]
33. 2-Chlorostyrene ----> (2R,3S)-cis-6-Chloro-1-vinylcyclohexa-4,6-diene-2,3-diol [13]
34. 2-Bromostyrene ----> (2R,3S)-cis-5-Bromo-1-vinylcyclohexa-4,6-diene-2,3-diol [13]
35. 2-Bromostyrene ----> (1R)-1-(4-Bromophenyl)-1,2-ethanediol [14]
36. 3-Chlorostyrene ----> cis-1-Chloro-5-vinylcyclohexa-4,6-diene-2,3-diol [13]
37. Ethynylbenzene ----> 3-Ethynyl-cis-1,2-dihydroxycyclohexa-3,5-diene [10]
38. [1,3-Dimethylbenzene] ----> 3,5-Dimethyl-cis-1,2-dihydroxycyclohexa-3,5-diene [15]
39. 1,4-Dimethylbenzene ----> 3,6-Dimethyl-cis-1,2-dihydroxycyclohexa-3,5-diene [15]
40. Ethyl Benzene ----> 3-Ethyl-cis-1,2-dihydroxycyclohexa-3,5-diene [16]
41. Phenylethanol ----> cis-2,3-Dihydroxy-2,3-dihydro-phenylethanol [16]
42. Acetophenone ----> 3-Acetyl-cis-1,2-dihydroxycyclohexa-3,5-diene [16]
43. Trifluorotoluene ----> Trifluorotoluene-cis-2,3-dihydrodiol [17]
44. Trifluoromethoxybenzene ----> Trifluoromethoxybenzene-cis-2,3-dihydrodiol [18]
45. Anisole ----> 3-Methoxy-cis-1,2-dihydroxycyclohexa-3,5-diene [19]
46. Phenetole ----> 3-Ethoxy-cis-1,2-dihydroxycyclohexa-3,5-diene [19]
47. (E)-beta-Bromostyrene ----> (E)-beta-Bromostyrene-cis-2,3-dihydrodiol [20]
48. (Z)-beta-Bromostyrene ----> (Z)-beta-Bromostyrene-cis-2,3-dihydrodiol [20]
49. 4-Bromotoluene ----> 4-Bromotoluene-cis-2,3-dihydrodiol [21]
50. trans-Cinnamonitrile ----> (trans-Cinnamonitrile)-cis-2,3-dihydrodiol [22]
51. Cyanobenzene ----> cis-2,3-cyanobenzene-dihydrodiol [21]
52. 1,2-Dichlorobenzene ----> 1,2-Dichlorobenzene-cis-3,4-dihydrodiol [21]
53. 1,3-Dichlorobenzene ----> 1,3-Dichlorobenzene-cis-4,5-dihydrodiol [21]
54. 1,4-Dichlorobenzene ----> 1,4-Dichlorobenzene-cis-2,3-dihydrodiol [21]
55. Fluorobenzene ----> cis-(1S,2S)-1,2-Dihydro-3-fluorocatechol [21]
56. 2-Methylphenol ----> 2-Methylcatechol [21]
57. 3-Methylphenol ----> 3-Methylcatechol [21]
58. 4-Methylphenol ----> 4-Methylcatechol [21]
59. Methyl p-tolyl sulfide ----> cis-2,3-Dihydroxy-2,3-dihydro-1-methyl-4-(methylthio)-benzene [23]
60. 4-Nitrotoluene ----> 3-Methyl-6-nitrocatechol [24]
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Monooxygenation
No. Reactions Refs
61. 1,2-Dimethylbenzene ----> 2,3-Dimethylphenol [21]
62. 1,3-Dimethylbenzene ----> 2,4-Dimethylphenol [21]
63. 2-Nitrotoluene ----> 2-Nitrobenzyl alcohol [24]
64. 3-Nitrotoluene ----> 3-Nitrobenzyl alcohol [24]
65. 4-Nitrotoluene ----> 2-Methyl-5-nitrophenol [24]
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Sulfoxidation
No. Reactions Refs
66. Ethyl phenyl sulfide ----> Ethyl phenyl sulfoxide [23]
67. p-Methoxyphenyl methyl sulfide ----> p-Methoxyphenyl methyl sulfoxide [23]
68. Methyl p-nitrophenyl sulfide ----> Methyl p-nitrophenyl sulfoxide [23]
69. Methyl phenyl sulfide ----> Methyl phenyl sulfoxide [23]
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B. Acts on Fused Aromatics
No. Reactions Refs
70. 2-Methoxynaphthalene ----> cis-1,2-Dihydroxy-1,2-dihydro-7-methoxynaphthalene [25]
71. 2-Methoxynaphthalene ----> cis-1,2-Dihydroxy-1,2-dihydro-6-methoxynaphthalene [25]
72. 2-Methoxynaphthalene ----> cis-1,2-Dihydroxy-1,2-dihydro-3-methoxynaphthalene [25]
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C. Acts on Linked Aromatics
No. Reactions Refs
73. Biphenyl ----> cis-1,2-dihydroxy-1,2-dihydro-biphenyl [26]
74. 2-Methoxybiphenyl ----> 3-(2-Methoxyphenyl)-(1S,2R)-3,5-cyclohexadiene-1,2-diol [26]
75. 2,3-Dimethoxybiphenyl ----> 3-(2,3-Dimethoxybiphenyl)-(1S,2R)-3,5-cyclohexadiene-1,2- diol [26]
76. 1,2-Methylenedioxy-biphenyl ----> 3-(1,2-Methylenedioxyphenyl)-3,5-cyclohexadiene-1,2-diol [27]
77. 2-Chlorobiphenyl ----> 2-Chlorobiphenyl-cis-2',3'-dihydrodiol [21]
78. 3-Chlorobiphenyl ----> 3-Chlorobiphenyl-cis-2',3'-dihydrodiol [21]
79. 4-Chlorobiphenyl ----> 4-Chlorobiphenyl-cis-2',3'-dihydrodiol [21]
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D. Acts on Aliphatic Olefins
Allylic methyl group monooxygenation
No. Reactions Refs
80. cis-1-Chloro-1-propene ----> cis-3-Chloro-2-propene-1-ol [28]
81. trans-1-Chloro-1-propene ----> trans-3-Chloro-2-propene-1-ol [28]
82. cis-1-Bromo-1-propene ----> cis-3-Bromo-2-propene-1-ol [28]
83. trans-1-Bromo-1-propene ----> trans-3-Bromo-2-propene-1-ol [28]
84. cis-2-Chloro-2-butene ----> cis-2-Chloro-2-butene-1-ol [28]
85. trans-2-Chloro-2-butene ----> trans-2-Chloro-2-butene-1-ol [28]
86. 1-Chloro-2-methyl-propene ----> 3-Chloro-2-methyl-2-propene-1-ol [28]
87. 1,1-Dichloro-1-propene ----> 3,3-Dichloro-2-propene-1-ol [28]
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Monooxygenation with allylic rearrangement
No. Reactions Refs
88. 2,3-Dichloro-1-propene ----> 2,3-dichloro-2-propene-1-ol [28]
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Dioxygenation
No. Reactions Refs
89. Trichloroethylene (TCE) ----> Glyoxylate [Reaction] [28]
90. Trichloroethylene (TCE) ----> Formate [Reaction] [28]
91. cis-1,4-Dichloro-2-butene ----> 1,4-Dichlorobutane-2,3-diol [28]
92. trans-1,4-Dichloro-2-butene ----> 1,4-Dichloro-2-butanone [28]
93. 1,1-Dichloroethene ----> ND [28]
94. cis-1,2-Dichloroethene ----> ND [28]
95. cis-Dibromoethene ----> ND [28]
96. trans-Dibromoethene ----> ND [28]
97. 3,4-Dichloro-1-butene ----> 3,4-Dichlorobutane-1,2-diol [28]
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E. Acts on Miscellaneous Substrates
No. Reactions Refs
98. Indan ----> (+)-(1S)-Indanol [21]
99. 2-Indanone ----> (S)-2-Hydroxy-1-indanone [29]
100. Indene ----> (+)-(1S)-Indenol [21]
101. Indene ----> 1-Indenol [21]
102. Indene ----> cis-(1R,2S)-Indandiol [1]
103. Indole ----> Indigo [21]
104. 1,2-Dihydronaphthalene ----> (+)-(1R)-Hydroxy-1,2-dihydro-naphthalene [30]
105. 1,2-Dihydronaphthalene ----> (+)-cis-(1S,2R)-dihydroxy-1,2,3,4-tetrahydronaphthalene [30]
106. 1,2-Dihydronaphthalene ----> (+)-cis-(1R,2S)-naphthalene dihydrodiol [30]
107. 1,2-Dihydronaphthalene ----> Naphthalene [30]
108. Benzocyclohept-1-ene ----> (+)-(5R)-Hydroxy-benzocyclohept-1-ene [31]
109. Benzocyclohept-1-ene ----> (+)-cis-(1S,2R)-dihydroxy-benzocycloheptane [31]
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References ([Abstract] links to a PubMed abstract)

  1. Wackett LP, Kwart LD, Gibson DT Biochemistry (1988) 27(4): 1360-7. [Abstract]

  2. Gibson DT, Cardini GE, Maseles FC, Kallio RE Biochemistry (1970) 9 (7): 1631-5. [Abstract]

  3. Boyd DR, Sharma ND, Byrne B, Hand MV, Malone JF, Sheldrake GN, Blacker J, Dalton HJ J Chem Soc, Perkin Trans 1 (1998): 1935.

  4. Boyd DR, Sharma ND, Barr SA, Dalton H, Chima J, Whited G, Seemayer R J Am Chem Soc (1994) 116:1147.

  5. Boyd DR, Sharma ND, Hand MV, Groocock MR, Kerley NA, Dalton H, Chima J, Sheldrake GN J Chem Soc, Chem Commun (1993): 974.

  6. Hudlicky T, Gonzalez D, Stabile M, Endoma MA, Deluca M, Parker D, Gibson DT, Resnick SM, Whited GM J Fluor Chem (1998) 89:23.

  7. Hudlicky T, Gonzalez D, Martinot T Tetrahedron Lett (1999): 3077.

  8. Hudlicky T, Seoane G, Price JD, Gadamasetti KG Synlett (1990): 433.

  9. Ziffer H, Kabuto K, Gibson DT, Kobal VM, Jerina DM Tetrahedron (1977) 33: 2491.

  10. Stabile MR, Hudlicky T, Meisels ML Tetrahedron: Asymmetry (1995) 6: 537.

  11. Hudlicky T, Endoma MAA, Butora G J chem Soc, Perkin Trans 1 (1996): 2187.

  12. Stabile MR, Hudlicky T, Meisels ML, Butora G, Gum AG, Feanley SP, Thorpe AJ, Ellis MR Chirality (1995) 7: 556.

  13. Hudlicky T, Boros EE, Boros CH Tetrahedron: Asymmetry (1993) 4: 1365.

  14. Konigsberger K, Hudlicky T Tetrahedron: Asymmetry (1993) 4: 2469.

  15. Gibson DT, Mahadevan V, Davey JF J Bacteriol (1974) 119(3): 930-6. [Abstract]

  16. Gibson DT, Gschwendt B, Yeh WK, Kobal VM Biochemistry (1973) 12(8): 1520-8. [Abstract]

  17. Nadeau LJ, Sayler GS, Spain JC Arch Microbiol (1998) 171(1): 44-9 [Abstract]

  18. Resnick SM, Gibson DT. Unpublished results.

  19. Resnick SM, Gibson DT Biodegradation (1993) 4: 195.

  20. Bennett HN, Hudlicky T Tetrahedron: Asymmetry (1999) 10: 2067-69.

  21. Gibson DT, Zylstra GJ, Chauhan S (1990) Biotransformations catalyzed by toluene dioxygenase from Pseudomonas putida F1. In (eds., Silver S, Chakrabarty AN, Iglewski B, Kaplan S) Pseudomonas: Biotransformations, Pathogenesis and Evolving Biotechnology. ASM Press, Washington DC pp. 121-132.

  22. Keener WK, Watwood ME, Apel WA Appl Microbiol Biotechnol (1998) 49(4): 455-62. [Abstract]

  23. Lee K, Brand JM, Gibson DT Biochem Biophys Res Commun (1995) 212(1): 9-15. [Abstract]

  24. Robertson JB, Spain JC, Haddock JD, Gibson DT Appl Environ Microbiol (1992) 58(8): 2643-8. [Abstract]

  25. Whited GM, Downie JC, Hudlicky T, Fearnley SP, Dudding TC, Olivo HF, Parker D Bioorg Med Chem (1994) 2(7): 727-34. [Abstract]

  26. Gonzalez D, Schapiro V, Seoane G, Hudlicky T Tetrahedron: Asymmetry (1999) 8: 975.

  27. Hudlicky T, Gonzalez D, Schiling S. Unpublished results.

  28. Lange CC, Wackett LP J Bacteriol (1997) 179(12): 3858-65. [Abstract]

  29. Resnick SM, Torok DS, Lee K, Brand JM, Gibson DT Appl Environ Microbiol (1994) 60(9): 3323-8. [Abstract]

  30. Torok DS, Resnick SM, Brand JM, Cruden DL, Gibson DT J Bacteriol (1995) 177(20): 5799-805. [Abstract]

  31. Resnick SM, Gibson DT Appl Environ Microbiol (1996) 62(4): 1364-8. [Abstract]

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