Mechanism of anaerobic ether cleavage : conversion of 2-phenoxyethanol to phenol and acetaldehyde by Acetobacterium sp.

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2002
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Speranza, Giovanna
Orlandi, Maximilian
Morelli, Carlo F.
Manitto, Paolo
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Journal of Biological Chemistry. 2002, 277(14), pp. 11684-11690. ISSN 0021-9258. eISSN 1083-351X. Available under: doi: 10.1074/jbc.M111059200
Zusammenfassung

2-Phenoxyethanol is converted into phenol and acetate by a strictly anaerobic Gram-positive bacterium Acetobacterium strain LuPhet1. Acetate results from oxidation of acetaldehyde that is the early product of the biodegradation process (Frings, J., and Schink, B. (1994) Arch. Microbiol. 162, 199 204). Feeding experiments with resting cell suspensions and 2-phenoxyethanol bearing two deuterium atoms at either carbon of the glycolic moiety as substrate demonstrated that the carbonyl group of the acetate derives from the alcoholic function and the methyl group derives from the adjacent carbon. A concomitant migration of a deuterium atom from C-1 to C-2 was observed. These findings were confirmed by NMR analysis of the acetate obtained by fermentation of 2-phenoxy-[2-13C,1-2H2]ethanol, 2-phenoxy-[1-13C,1-2H2]ethanol, and 2-phenoxy-[1,2-13C2,1- 2H2]ethanol. During the course of the biotransformation process, the molecular integrity of the glycolic unit was completely retained, no loss of the migrating deuterium occurred by exchange with the medium, and the 1,2- deuterium shift was intramolecular. A diol dehydrataselike mechanism could explain the enzymatic cleavage of the ether bond of 2-phenoxyethanol, provided that an intramolecular H/OC6H5 exchange is assumed, giving rise to the hemiacetal precursor of acetaldehyde. However, an alternative mechanism is proposed that is supported by the well recognized propensity of α-hydroxyradical and of its conjugate base (ketyl anion) to eliminate a ß-positioned leaving group.

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ISO 690SPERANZA, Giovanna, Britta MÜLLER, Maximilian ORLANDI, Carlo F. MORELLI, Paolo MANITTO, Bernhard SCHINK, 2002. Mechanism of anaerobic ether cleavage : conversion of 2-phenoxyethanol to phenol and acetaldehyde by Acetobacterium sp.. In: Journal of Biological Chemistry. 2002, 277(14), pp. 11684-11690. ISSN 0021-9258. eISSN 1083-351X. Available under: doi: 10.1074/jbc.M111059200
BibTex
@article{Speranza2002Mecha-7470,
  year={2002},
  doi={10.1074/jbc.M111059200},
  title={Mechanism of anaerobic ether cleavage : conversion of 2-phenoxyethanol to phenol and acetaldehyde by Acetobacterium sp.},
  number={14},
  volume={277},
  issn={0021-9258},
  journal={Journal of Biological Chemistry},
  pages={11684--11690},
  author={Speranza, Giovanna and Müller, Britta and Orlandi, Maximilian and Morelli, Carlo F. and Manitto, Paolo and Schink, Bernhard}
}
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    <dcterms:abstract xml:lang="eng">2-Phenoxyethanol is converted into phenol and acetate by a strictly anaerobic Gram-positive bacterium Acetobacterium strain LuPhet1. Acetate results from oxidation of acetaldehyde that is the early product of the biodegradation process (Frings, J., and Schink, B. (1994) Arch. Microbiol. 162, 199 204). Feeding experiments with resting cell suspensions and 2-phenoxyethanol bearing two deuterium atoms at either carbon of the glycolic moiety as substrate demonstrated that the carbonyl group of the acetate derives from the alcoholic function and the methyl group derives from the adjacent carbon. A concomitant migration of a deuterium atom from C-1 to C-2 was observed. These findings were confirmed by NMR analysis of the acetate obtained by fermentation of 2-phenoxy-[2-13C,1-2H2]ethanol, 2-phenoxy-[1-13C,1-2H2]ethanol, and 2-phenoxy-[1,2-13C2,1- 2H2]ethanol. During the course of the biotransformation process, the molecular integrity of the glycolic unit was completely retained, no loss of the migrating deuterium occurred by exchange with the medium, and the 1,2- deuterium shift was intramolecular. A diol dehydrataselike mechanism could explain the enzymatic cleavage of the ether bond of 2-phenoxyethanol, provided that an intramolecular H/OC6H5 exchange is assumed, giving rise to the hemiacetal precursor of acetaldehyde. However, an alternative mechanism is proposed that is supported by the well recognized propensity of α-hydroxyradical and of its conjugate base (ketyl anion) to eliminate a ß-positioned leaving group.</dcterms:abstract>
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