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Title: Benzylic monooxygenation catalyzed by toluene dioxygenase from Pseudomonas putida

Abstract

Toluene dioxygenase, a multicomponent enzyme system known to oxidize mononuclear aromatic hydrocarbons to cis-dihydrodiols, oxidized indene and indan to 1-indenol and 1-indanol, respectively. In addition, the enzyme catalyzed dioxygen addition to the nonaromatic double bond of indene to form cis-1,2-indandiol. The oxygen atoms in 1-indenol and cis-1,2-indandiol were shown to be derived from molecular oxygen, whereas 70% of the oxygen in 1-indanol was derived from water. All of the isolated products were optically active as demonstrated by /sup 19/F NMR and HPLC discrimination of diastereomeric esters and by chiroptic methods. The high optical purity of (-)-(1R)-indanol (84% enantiomeric excess) and the failure of scavengers of reactive oxygen species to inhibit the monooxygenation reaction supported the contention that monooxygen insertion is mediated by an active-site process. Experiments with 3-(/sup 2/H) indene indicated that equilibration between C-1 and C-3 occurred prior to the formation of the carbon-oxygen bond to yield 1-indenol. Naphthalene dioxygenase also oxidized indan to 1-indanol, which suggested that benzylic monoxygenation may be typical of this group of dioxygenases.

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Texas, Austin (USA)
OSTI Identifier:
5410589
Resource Type:
Journal Article
Journal Name:
Biochemistry; (United States)
Additional Journal Information:
Journal Volume: 27:4
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 62 RADIOLOGY AND NUCLEAR MEDICINE; INDAN; OXIDATION; INDENE; OXYGENASES; NUCLEAR MAGNETIC RESONANCE; AROMATICS; FLUORINE 19; GLYCOLS; HYDROCARBONS; LIQUID COLUMN CHROMATOGRAPHY; PROTONS; PSEUDOMONAS; STEREOCHEMISTRY; TOLUENE; ALCOHOLS; ALKYLATED AROMATICS; BACTERIA; BARYONS; CHEMICAL REACTIONS; CHROMATOGRAPHY; CONDENSED AROMATICS; ELEMENTARY PARTICLES; ENZYMES; FERMIONS; FLUORINE ISOTOPES; HADRONS; HYDROXY COMPOUNDS; ISOTOPES; LIGHT NUCLEI; MAGNETIC RESONANCE; MICROORGANISMS; NUCLEI; NUCLEONS; ODD-EVEN NUCLEI; ORGANIC COMPOUNDS; OXIDOREDUCTASES; RESONANCE; SEPARATION PROCESSES; STABLE ISOTOPES; 550201* - Biochemistry- Tracer Techniques; 550601 - Medicine- Unsealed Radionuclides in Diagnostics

Citation Formats

Wackett, L P, Kwart, L D, and Gibson, D T. Benzylic monooxygenation catalyzed by toluene dioxygenase from Pseudomonas putida. United States: N. p., 1988. Web. doi:10.1021/bi00404a041.
Wackett, L P, Kwart, L D, & Gibson, D T. Benzylic monooxygenation catalyzed by toluene dioxygenase from Pseudomonas putida. United States. https://doi.org/10.1021/bi00404a041
Wackett, L P, Kwart, L D, and Gibson, D T. 1988. "Benzylic monooxygenation catalyzed by toluene dioxygenase from Pseudomonas putida". United States. https://doi.org/10.1021/bi00404a041.
@article{osti_5410589,
title = {Benzylic monooxygenation catalyzed by toluene dioxygenase from Pseudomonas putida},
author = {Wackett, L P and Kwart, L D and Gibson, D T},
abstractNote = {Toluene dioxygenase, a multicomponent enzyme system known to oxidize mononuclear aromatic hydrocarbons to cis-dihydrodiols, oxidized indene and indan to 1-indenol and 1-indanol, respectively. In addition, the enzyme catalyzed dioxygen addition to the nonaromatic double bond of indene to form cis-1,2-indandiol. The oxygen atoms in 1-indenol and cis-1,2-indandiol were shown to be derived from molecular oxygen, whereas 70% of the oxygen in 1-indanol was derived from water. All of the isolated products were optically active as demonstrated by /sup 19/F NMR and HPLC discrimination of diastereomeric esters and by chiroptic methods. The high optical purity of (-)-(1R)-indanol (84% enantiomeric excess) and the failure of scavengers of reactive oxygen species to inhibit the monooxygenation reaction supported the contention that monooxygen insertion is mediated by an active-site process. Experiments with 3-(/sup 2/H) indene indicated that equilibration between C-1 and C-3 occurred prior to the formation of the carbon-oxygen bond to yield 1-indenol. Naphthalene dioxygenase also oxidized indan to 1-indanol, which suggested that benzylic monoxygenation may be typical of this group of dioxygenases.},
doi = {10.1021/bi00404a041},
url = {https://www.osti.gov/biblio/5410589}, journal = {Biochemistry; (United States)},
number = ,
volume = 27:4,
place = {United States},
year = {Tue Feb 23 00:00:00 EST 1988},
month = {Tue Feb 23 00:00:00 EST 1988}
}