Thermal decomposition of the tert-butyl perester of thymidine-5′-carboxylic acid. Formation and fate of the pseudo-C4′ radical

• Published in: Tetrahedron Vol. 60; no. 19; pp. 4303 - 4308
• Main Authors: Montevecchi, Pier Carlo, Manetto, Antonio, Navacchia, Maria Luisa, Chatgilialoglu, Chryssostomos
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 03.05.2004; Elsevier
• Subjects: Cage decomposition; Chemistry; Chemistry, Organic; DNA damage; Nucleoside; Physical Sciences; Radical decomposition; Science & Technology; Thymidine; Thymidine-5′-carboxylic acid tert-butyl perester; Nucleoside; Thymidine; Thymidine-5′-carboxylic acid tert-butyl perester; Radical decomposition; Cage decomposition; DNA damage; cage decomposition; OXIDATION; DINUCLEOSIDE; radical decomposition; DNA; NUCLEOSIDES; nucleoside; thymidine; thymidine-5 '-carboxylic acid tert-butyl perester; DAMAGE
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2004.03.029

Thermal decomposition of the tert-butyl perester of thymidine-5′-carboxylic acid 1 carried out at 85 °C in different solvents affords the tert-butylacetal 4a , deriving from in cage decomposition, and pseudo C4′ radicals 2 . Radicals 2 can be reduced to 5 by hydrogen atom abstraction from thiol (thiophenol or glutathione) or THF, or can be oxidized to cations 8 by dioxygen or perester 1 itself. Cations 8 are stereoselectively trapped by the nucleophilic solvent ( tert-butanol, methanol, water) to give acetals 4a- c . Graphic