학술논문
Synthesis and Structural Characteristics of all Mono- and Difluorinated 4,6-Dideoxy-d- xylo -hexopyranoses.
Document Type
Academic Journal
Author
Wheatley DE; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Fontenelle CQ; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Kuppala R; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Szpera R; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Briggs EL; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Vendeville JB; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Wells NJ; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Light ME; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.; Linclau B; School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.
Source
Publisher: American Chemical Society Country of Publication: United States NLM ID: 2985193R Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-6904 (Electronic) Linking ISSN: 00223263 NLM ISO Abbreviation: J Org Chem Subsets: MEDLINE
Subject
Language
English
Abstract
Protein-carbohydrate interactions are implicated in many biochemical/biological processes that are fundamental to life and to human health. Fluorinated carbohydrate analogues play an important role in the study of these interactions and find application as probes in chemical biology and as drugs/diagnostics in medicine. The availability and/or efficient synthesis of a wide variety of fluorinated carbohydrates is thus of great interest. Here, we report a detailed study on the synthesis of monosaccharides in which the hydroxy groups at their 4- and 6-positions are replaced by all possible mono- and difluorinated motifs. Minimization of protecting group use was a key aim. It was found that introducing electronegative substituents, either as protecting groups or as deoxygenation intermediates, was generally beneficial for increasing deoxyfluorination yields. A detailed structural study of this set of analogues demonstrated that dideoxygenation/fluorination at the 4,6-positions caused very little distortion both in the solid state and in aqueous solution. Unexpected trends in α/β anomeric ratios were identified. Increasing fluorine content always increased the α/β ratio, with very little difference between regio- or stereoisomers, except when 4,6-difluorinated.