Isolation and characterization of (+)-1,1a-dihydroxy-1-hydrofluoren-9-one formed by angular dioxygenation in the bacterial catabolism of fluorene.
Transformation of fluorene by washed cells of fluorene-grown Pseudomonas sp. F274 yielded 1,la-dihydroxy-1-hydrofluoren-9-one (up to 100 mg/l) as the stable product of angular dioxygenation of 9-fluorenone. Structural identity of the angular keto-diol was established by 13C- and 1H-NMR, gas chromatography- and direct probe-mass spectrometry. Definitive assignment of 1,1a-dioxygenation, but not 4,4a-, was based on the isolation and rigorous identification of 1-hydroxyfluoren-9-one as the exclusive product of acidic dehydration. Chiral 1H-NMR analysis and optical rotation of isolated 1,1a-dihydroxy-1-hydrofluoren-9-one ([alpha]D = + 132.1 degrees) are indicative of a single enantiomer with an inferred cis-stereochemistry of the hydroxyl groups. This compound is evidently an intermediate of fluorene catabolism by this strain and not a dead-end product because its formation is transient in washed cell incubations and ultimately it is completely consumed with the formation of acidic metabolites.
Selifonov
S A
SA
Center for Environmental Diagnostics and Bioremediation, University of West Florida, Pensacola 32514.
Grifoll
M
M
Gurst
J E
JE
Chapman
P J
PJ
D005449:Fluorenes / Q000737:chemistry / Q000302:isolation & purification* / Q000378:metabolism*; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D010100:Oxygen / Q000378:metabolism*; D011549:Pseudomonas / Q000378:metabolism*; D013237:Stereoisomerism
D005449:Fluorenes; C081458:1,1a-dihydroxy-1-hydrofluoren-9-one; D010100:Oxygen