Total syntheses of conformationally locked difluorinated pentopyranose analogues and a pentopyranosyl phosphate mimetic.
Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate.
Miles
Jonathan A L
JA
Department of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, U.K.
Mitchell
Lisa
L
Percy
Jonathan M
JM
Singh
Kuldip
K
Uneyama
E
E
D018360:Crystallography, X-Ray; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis*; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D018716:Molecular Mimicry; D010084:Oxidation-Reduction; D000644:Quaternary Ammonium Compounds / Q000737:chemistry
D006574:Heterocyclic Compounds, 2-Ring; D006845:Hydrocarbons, Fluorinated; D007202:Indicators and Reagents; D000644:Quaternary Ammonium Compounds