Time-resolved resonance Raman investigation of the 2-fluorenylnitrenium ion reactions with C8 guanosine derivatives.
A nanosecond time-resolved resonance Raman (ns-TR3) spectroscopic study of the reactions of the 2-fluorenylnitrenium ion with several C8-substituted guanosine derivatives is reported. The TR3 spectra show that the 2-fluorenylnitrenium ion reacts with the C8-substituted guanosine derivatives (C8-methylguanosine and C8-bromoguanosine) to produce C8 intermediates with the methyl and bromine moieties still attached to the intermediate species at the C8 position. The C8-bromoguanosine species was observed to be less reactive toward the 2-fluorenylnitrenium ion compared to the guanosine and C8-methylguanosine species. Comparison of the TR3 spectra to the results obtained from density functional theory calculations was used to characterize the C8 intermediates observed to learn more about their structure and properties. The implications of these results for the chemical reactivity of arylnitrenium ions toward substituted guanosine derivatives are briefly discussed.
Xue
Jiadan
J
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, PR China.
Chan
Pik Ying
PY
Du
Yong
Y
Guo
Zhen
Z
Chung
Cecilia Wan Ying
CW
Toy
Patrick H
PH
Phillips
David Lee
DL
D005449:Fluorenes / Q000737:chemistry*; D006151:Guanosine / Q000031:analogs & derivatives* / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008968:Molecular Conformation; D010782:Photolysis; D012015:Reference Standards; D013059:Spectrum Analysis, Raman / Q000379:methods* / Q000592:standards; D013237:Stereoisomerism; D013997:Time Factors
C525234:2-fluorenylnitrenium; D005449:Fluorenes; D007477:Ions; D006151:Guanosine