Thermal decomposition of the tert-butyl perester of thymidine-5′-carboxylic acid. Formation and fate of the pseudo-C4′ radical
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 (thi...
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Published in | Tetrahedron Vol. 60; no. 19; pp. 4303 - 4308 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
OXFORD
Elsevier Ltd
03.05.2004
Elsevier |
Subjects | |
Online Access | Get full text |
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Summary: | 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
.
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ISSN: | 0040-4020 1464-5416 |
DOI: | 10.1016/j.tet.2004.03.029 |