The beta-fluorine effect. Electronic versus steric effects in radical deoxygenations of fluorine-containing pentofuranose nucleosides.
Stereoselective pyramidalization of free radicals by a vicinal fluorine substituent, the beta-fluorine effect, was invoked to rationalize a 77:23 anti/syn ratio of 2-deuterio-1-fluorocyclopentanes obtained by radical reduction of trans-2-fluoro-1-bromocyclopentane with tributyltin deuteride (Dolbier, W. R., Jr.; Bartberger, M. D. J. Org. Chem. 1995, 60, 4984-4985). We have evaluated analogous reductions of the four possible stereoisomers of some adenine 2'(3')-fluoro-3'(2')-O-phenoxythiocarbonyl nucleoside derivatives. In all cases, the steric effect of adenine on the beta face directs deuterium transfer from the stannane to C2'(C3') on the alpha face of the furanose ring. However, the beta-fluorine effect enhances ratios of deuterium transfer anti to the vicinal fluorine substituent.
Wnuk
Stanislaw F
SF
Department of Chemistry, Florida International University, Miami 33199, USA.
Companioni
Dania R
DR
Neschadimenko
Vladimir
V
Robins
Morris J
MJ
D000225:Adenine / Q000031:analogs & derivatives* / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009705:Nucleosides / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013871:Thiones / Q000138:chemical synthesis*
D005609:Free Radicals; D009705:Nucleosides; D017646:Organosilicon Compounds; D013871:Thiones; D005461:Fluorine; D000225:Adenine; D010100:Oxygen