A Chiroptical Switch Owing to Mercury-Crosslinked Ribonucleosides
Vladimír Sychrovský1, Miloš Buděšínský1, Ivan Rosenberg1
1Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo náměstí 2, Praha, 16000Czech Republic.
Abstract:
A highly specific chiroptical response of ribonucleoside diastereomers upon metallic crosslinking was demonstrated by Raman optical activity (ROA) spectroscopy. Three ROA diagnostic bands, assigned to prominent in-plane nucleobase ring deformations, undergo a concerted sign inversion upon mercury crosslinking. Virtually the same ROA sign switch was also observed upon a stereochemical modification (N1-glycosidic bond inversion) of a metal-free ribonucleoside. The prominent ROA sign switch thereby exemplified congruous chiroptical responses, owing to metal crosslinking and distinct ribonucleoside stereochemical modification. It is the first ROA detection of a metal-mediated base pair in mercury-crosslinked ribonucleosides evidenced by the ESI-MS and NMR measurements.
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