Mechanism of anaerobic ether cleavage: conversion of 2-phenoxyethanol to phenol and acetaldehyde by Acetobacterium sp.
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-(13)C,1-(2)H(2)]ethanol, 2-phenoxy-[1-(13)C,1-(2)H(2)]ethanol, and 2-phenoxy-[1,2-(13)C(2),1-(2)H(2)]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 dehydratase-like mechanism could explain the enzymatic cleavage of the ether bond of 2-phenoxyethanol, provided that an intramolecular H/OC(6)H(5) 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 alpha-hydroxyradical and of its conjugate base (ketyl anion) to eliminate a beta-positioned leaving group.
Speranza
Giovanna
G
Dipartimento di Chimica Organica e Industriale, Università degli Studi di Milano, and Centro di Studio per le Sostanze Organiche Naturali, CNR, via Venezian 21, I-20133 Milano, Italy. giovanna.speranza@unimi.it
Mueller
Britta
B
Orlandi
Maximilian
M
Morelli
Carlo F
CF
Manitto
Paolo
P
Schink
Bernhard
B
D000079:Acetaldehyde / Q000378:metabolism*; D000838:Anions; D002855:Chromatography, Thin Layer; D005026:Ethylene Glycols / Q000378:metabolism*; D016987:Gram-Positive Rods / Q000737:chemistry / Q000378:metabolism*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D010100:Oxygen / Q000378:metabolism*; D019800:Phenol / Q000378:metabolism*
D000838:Anions; D005026:Ethylene Glycols; D019800:Phenol; D000079:Acetaldehyde; C005398:phenoxyethanol; D010100:Oxygen