1H-NMR and mass spectrometric studies of tetrahydropterins. Evidence for the structure of 6-pyruvoyl tetrahydropterin, an intermediate in the biosynthesis of tetrahydrobiopterin.
The conversion of dihydroneopterin triphosphate in the presence of 6-pyruvoyl tetrahydropterin synthase was followed by 1H-NMR spectroscopy. The interpretation of the spectra of the product is unequivocal: they show formation of a tetrahydropterin system carrying a stereospecifically oriented substituent at the asymmetric C(6) atom. The spectra are compatible with formation of a (3')-CH3 function, and with complete removal of the 1' and 2' hydrogens of dihydroneopterin triphosphate. The fast-atom-bombardment/mass spectrometry study of the same product yields a [M + H]+ ion at m/z 238 compatible with the structure of 6-pyruvoyl tetrahydropterin. The data support the proposed structure of 6-pyruvoyl tetrahydropterin as a key intermediate in the biosynthesis of tetrahydrobiopterin.
Faculty of Biology, University of Konstanz, Federal Republic of Germany.
S
S
Ghisla
T
T
Kuster
P
P
Steinerstauch
W
W
Leimbacher
W J
WJ
Richter
F
F
Raschdorf
R
R
Dahinden
H C
HC
Curtius
D000429:Alcohol Oxidoreductases / Q000378:metabolism; D001708:Biopterins / Q000031:analogs & derivatives* / Q000096:biosynthesis; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008956:Models, Chemical; D019798:Neopterin / Q000031:analogs & derivatives; D010084:Oxidation-Reduction; D019761:Phosphorus-Oxygen Lyases; D011621:Pteridines / Q000378:metabolism; D011622:Pterins / Q000032:analysis; D013237:Stereoisomerism
D011621:Pteridines; D011622:Pterins; C011552:tetrahydropterin; C013490:dihydroneopterin triphosphate; D001708:Biopterins; D019798:Neopterin; C045652:dyspropterin; D000429:Alcohol Oxidoreductases; D019761:Phosphorus-Oxygen Lyases; C043497:6-pyruvoyltetrahydropterin synthase; C003402:sapropterin