Characterization of 5-Hydroxy-8-oxo-7,8-dihydroguanosine in the Photosensitized Oxidation of 8-Oxo-7,8-dihydroguanosine and Its Rearrangement to Spiroiminodihydantoin
- 1 December 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (51), 16777-16782
- https://doi.org/10.1021/ja030678p
Abstract
The photosensitized oxidation of 2',3',5'-tris-(O-tert-butyldimethylsilyl)-8-oxo-7,8-dihydroguansine (8-oxoG) with singlet oxygen was studied by low-temperature NMR. A stable intermediate was characterized at -60 degreesC by C-13, 2D NMR HMBC spectra, and chemical shifts calculated by hybrid Hallree-Fock density functional theory which agreed with the structure 5-hydroperoxy-8-oxo-7,8-dihydroquanosine. Reduction of this intermediate at low temperature afforded the corresponding alcohol, the long-postulated 5-hydroxy8-oxo-7,8-dihydroguanosine, the last intermediate in the formation of spiroiminodihydantoin. Upon warming to room temperature, this alcohol rearranges to form the spiroiminodihydantoin in good yield within 2 h.This publication has 28 references indexed in Scilit:
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