TY - JOUR
T1 - The reaction of nucleophilic species with quinonoid 6,6,7,7-tetramethyldihydropterin
AU - Noar, J. B.
AU - Venkataram, U. V.
AU - Bruice, Thomas C.
AU - Bollag, G.
AU - Whittle, R.
AU - Sammons, D.
AU - Henry, R.
AU - Benkovic, Stephen J.
N1 - Funding Information:
This work was supported by grants to T.C.B. from the National Institutes of Health and to S.J.B. from the National Science Foundation.
PY - 1986/3
Y1 - 1986/3
N2 - The products, kinetics, and mechanisms for the reaction of HO-, NH2OCH3, and HOCl with 1,5-quinonoid 6,6,7,7-tetramethyldihydropterin are provided. The reaction with hydroxide leads to a rearranged imidazolone whose structure was proved by independent synthesis. With methoxylamine the product is a dihydro adduct derived from methoxylamine displacement of the 2-amino group. In this case the structure of the product was obtained via X-ray crystallography and 13C NMR with the former providing novel information about the tautomeric form of this pterin quinonoid species. The chlorination of the quinonoid generates N2 or N3 chloroamines based on high-resolution mass spectrometric analysis. Mechanisms for these transformations are proposed.
AB - The products, kinetics, and mechanisms for the reaction of HO-, NH2OCH3, and HOCl with 1,5-quinonoid 6,6,7,7-tetramethyldihydropterin are provided. The reaction with hydroxide leads to a rearranged imidazolone whose structure was proved by independent synthesis. With methoxylamine the product is a dihydro adduct derived from methoxylamine displacement of the 2-amino group. In this case the structure of the product was obtained via X-ray crystallography and 13C NMR with the former providing novel information about the tautomeric form of this pterin quinonoid species. The chlorination of the quinonoid generates N2 or N3 chloroamines based on high-resolution mass spectrometric analysis. Mechanisms for these transformations are proposed.
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U2 - 10.1016/0045-2068(86)90014-3
DO - 10.1016/0045-2068(86)90014-3
M3 - Article
AN - SCOPUS:1542637040
SN - 0045-2068
VL - 14
SP - 17
EP - 27
JO - Bioorganic Chemistry
JF - Bioorganic Chemistry
IS - 1
ER -