Synthesis and structural characteristics of all mono- and difluorinated 4,6-dideoxy-d-xylo-hexopyranoses
| Autor: | Bruno Linclau, Jean-Baptiste Vendeville, Clement Q. Fontenelle, Robert Szpera, Mark E. Light, Ramakrishna Kuppala, Edward L Briggs, David E Wheatley, Neil J. Wells |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Aqueous solution Anomer 010405 organic chemistry Stereochemistry Organic Chemistry Chemical biology chemistry.chemical_element Carbohydrate 010402 general chemistry 01 natural sciences 0104 chemical sciences chemistry Fluorine Monosaccharide Protecting group Deoxygenation |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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