Synthesis and incorporation into PNA of fluorinated olefinic PNA (F-OPA) monomers.
[structure: see text] A fluorinated OPA monomer containing the base thymine ((Z)-t-F-OPA) was synthesized in 12 steps, featuring a highly selective allylic over homoallylic Mitsunobu substitution for the introduction of the nucleobase. F-OPA modified PNA decamers were prepared by the MMTr/acyl protection strategy. The thermal stability of duplexes of PNA decamers containing (Z)-t-F-OPA units with antiparallel complementary DNA was measured. We found a strong dependence of stability from the sequential position of the (Z)-t-F-OPA units, ranging from DeltaT(m) of +2.4 to -8.1 degrees C/modification relative to unmodified PNA.
Hollenstein
Marcel
M
Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
Leumann
Christian J
CJ
D000475:Alkenes / Q000138:chemical synthesis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D018076:DNA, Complementary / Q000138:chemical synthesis; D005461:Fluorine; D007202:Indicators and Reagents; D013058:Mass Spectrometry; D020135:Peptide Nucleic Acids / Q000138:chemical synthesis*; D013237:Stereoisomerism; D013941:Thymine / Q000737:chemistry; D014466:Ultraviolet Rays
D000475:Alkenes; D018076:DNA, Complementary; D007202:Indicators and Reagents; D020135:Peptide Nucleic Acids; D005461:Fluorine; D013941:Thymine