Selective generation and reactivity of 5'-adenosinyl and 2'-adenosinyl radicals.
The reaction of hydrated electrons (e(-)(aq) with 8-bromoadenosine 7 has been investigated by radiolytic methods coupled with product studies. Pulse radiolysis revealed that one-electron reductive cleavage of the C-Br bond gives the C8 radical 8 followed by a fast radical translocation to the sugar moiety. The reaction is partitioned between C5' and C2' positions in a 60:40 ratio leading to 5'-adenosinyl radical 9 and 2'-adenosinyl radical 11. This radical translocation from C8 to different sites of the sugar moiety has also been addressed computationally by means of DFT B3LYP calculations. In addition, ketone 21 was prepared and photolyzed providing an independent generation of C2' radical 11. Both C5' and C2' radicals undergo unimolecular reactions. Radical 9 attacks adenine with a rate constant of 1.0 x 10(4) s(-1) and gives the aromatic aminyl radical 10, whereas C2' radical 11 liberates adenine with a rate constant of 1.1 x 10(5) s(-1).
ISOF, Consiglio Nazionale delle Ricerche, Via P Gobetti 101, 40129 Bologna, Italy. chrys@isof.cnr.it
Chryssostomos
C
Chatgilialoglu
Maria
M
Duca
Carla
C
Ferreri
Maurizio
M
Guerra
Marcella
M
Ioele
Quinto G
QG
Mulazzani
Harald
H
Strittmatter
Bernd
B
Giese
D000241:Adenosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D011830:Radiation Effects
D005609:Free Radicals; C036038:8-bromoadenosine; D000241:Adenosine