Total Syntheses of Conformationally Locked Difluorinated Pentopyranose Analogues and a Pentopyranosyl Phosphate Mimetic
journal contributionposted on 02.03.2007, 00:00 authored by Jonathan A. L. Miles, Lisa Mitchell, Jonathan M. Percy, Kuldip Singh, E. Uneyama
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.
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sequenceTotal Synthesesnovel bicyclic analoguesRCM reactionPentopyranosyl Phosphate MimeticTrifluoroethanolmetalated difluoroenolDifluorinated Pentopyranose AnaloguespentopyranoseWittigtransannular ring openingEpoxidationConformationallyglycosyl phosphatedihydroxylationdifluoroallylic alcoholtransannular hemiacetalizationpurificationcyclooctenone intermediatesrearrangement