Progress in the field of enantioselective electrophilic fluorination during the past eighteen years resulting from fascinating research conducted by twelve international groups is reviewed. Two complementary strategies for the synthesis of enantiopure fluorine-containing molecules currently define state-of-the-art in this area. The use of chiral, non-racemic fluorinating agents is the most general approach while catalytic methods using either transition-metal catalysts or organocatalysts apply to specific substrates.
The review demonstrates how carbohydrate chemists exploit the two fundamental strategies of organofluorine chemistry; (a) direct introduction of fluorine atom(s) or fluorinated groups by appropriate reagents in a late synthetic step, or (b) linking of fluorine-containing “building blocks“ with various reactants (including enantioselective approaches), in order to synthesize a wide variety of fluorinated sugars. Numerous representative examples of these strategies are provided and discussed. Also included are a number of recommended experimental procedures (provided at the end of sections 1-3). In addition to reviewing various convenient fluorinating reagents that have so far been applied to carbohydrate chemistry, the utility of glycosyl fluorides in chemical and enzymatic glycosylations are also examined.