The reaction of pyranoside 2-uloses with DAST revised. Synthesis of 1-fluoro-ketofuranosyl fluorides and their reactivity with alcohols

Recent Advances in Nucleophilic Fluorination Reactions of Organic Compounds­ Using Deoxofluor and DAST

“…Deoxofluor (1) and DAST (2) have been utilized for such molecules (Table 2). 6, [18][19][20][21][22][23][24][25][26][27][28][29]…”

Morpholinosulfur Trifluoride (Morph‐DAST)‐Mediated Rearrangement in the Fluorination of Cyclic α,α‐Dialkoxy Ketones toward 1,2‐Dialkoxy‐1,2‐difluorinated Compounds

“…[13] In contrast to alcohols, rearrangements of ketones have been less investigated. Fluorination of the C-2 of aldopyranosid-2-uloses with DAST leads to gem-difluorination products or gives 2,5-anhydro-1,2-difluorofuranoses as a result of a ring contraction reaction with concomitant introduction of fluorine at C-1 and C-2, [14] and does not lead to 2-alkoxy-1,2-difluorotetrahydropyrans via a 1,2-alkoxy migration as initially thought. [15] In contrast to the latter monoacetals of a-ketoaldehydes, the deoxofluorination of monoacetals of 1,2-diketones was not investigated before and it was decided to further investigate this reaction.…”

Highly-functionalised difluorinated (hydroxymethyl)conduritol analogues via the Diels–Alder reactions of a difluorinated dienophile

“…5 Complex mixtures of products can result, though some imaginative solutions have been developed to minimise competing pathways. 6 De novo methods using building blocks for the construction of difluorinated analogues of monosaccharides, carbasugars or cyclitols are not well established. There are successful strategies that deliver fluorinated 6-membered carbocycles based on free radical cyclisations 7 and intramolecular aldol reactions, 8 but the most obvious disconnection of highly-functionalised cyclohexane derivatives would rely on the availability of reliable Diels-Alder cycloaddition chemistry 9 based on either difluorinated dienes, 10 or difluorinated dienophiles.…”