{Generation of C-1′ radicals through a $\beta$-(acyloxy)alkyl rearrangement in modified purine and pyrimidine nucleosides}

Scientific publication - Journal Article uoadl:2960836 6 Read counter

Unit:
Department of Chemistry
Title:
{Generation of C-1′ radicals through a $\beta$-(acyloxy)alkyl rearrangement in modified purine and pyrimidine nucleosides}
Languages of Item:
English
Abstract:
The synthesis of protected 1',2'-didehydro-2'-deoxyadenosines has been optimized by incorporating a phosphoranylidene protection of the adenine amine function. These unsaturated adenosines have served as substrates for the electrophilic iodopivaloyloxylation leading to new nucleosides modified at the anomeric position. Reaction of halopivaloates 10, 11 and 12 with tributyltin hydride generates indirectly C-1' radicals through a $\beta$- (acyloxy)alkyl rearrangement. Rate constants for these rearrangements have been measured by using free-radical clock methodology and comparison of these data with previous reported results provides structural information about the nature of this important class of radicals.
Publication year:
1998
Authors:
Thanasis Gimisis
Giuseppina Ialongo
Chryssostomos Chatgilialoglu
Journal:
Tetrahedron
Publisher:
ELSEVIER BV
Volume:
54
Number:
3-4
Pages:
573--592
Main subject category:
Science
DOI:
10.1016/s0040-4020(97)10317-9
The digital material of the item is not available.