Still Elusive - Pd(II)-Mediated Base Pairing by an Acetophenone Oxime Palladacycle within N-15-Labelled Double-Helical Oligonucleotides




Toiviala Maaret, Kleemola Vesa, Maity Sajal, Lönnberg Tuomas

PublisherWILEY-V C H VERLAG GMBH

2023

European Journal of Organic Chemistry

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY

EUR J ORG CHEM

e202201443

26

10

11

1434-193X

1434-193X

DOIhttps://doi.org/10.1002/ejoc.202201443

https://doi.org/10.1002/ejoc.202201443

https://research.utu.fi/converis/portal/detail/Publication/179085134



Both α and β anomers of an acetophenone C-nucleoside were synthesized and incorporated in the middle of short oligodeoxynucleotides. The ketone oligonucleotides were converted to 15N-labelled oxime oligonucleotides by treatment with 15N-hydroxylamine and, finally, cyclopalladated by treatment with lithium tetrachloropalladate. Comparison of the UV melting profiles of duplexes bearing the β anomer of either the palladacyclic or the metal-free oxime C-nucleoside suggested formation of a stable Pd(II)-mediated base pair, especially with adenine or thymine as the base pairing partner. Melting profiles of the corresponding duplexes bearing the α anomer were much more convoluted, precluding meaningful comparison. 15N NMR spectra were obtained for the β anomeric oxime oligonucleotide as well as its palladacyclic derivative but the signals unfortunately diminished below detection limit when the latter was hybridized with a complementary strand placing a 15N3-labelled thymine opposite to the palladacyclic residue.


Last updated on 2024-26-11 at 21:03