Addition of Electrophilic Radicals to 2-Benzyloxyglycals: Synthesis and Functionalization of Fluorinated alpha-C-Glycosides and Derivatives

作者：Colombel Sophie; Van Hijfte Nathalie; Poisson Thomas; Leclerc Eric^*; Pannecoucke Xavier

来源：Chemistry - A European Journal, 2013, 19(38): 12778-12787.

DOI：10.1002/chem.201302070

• fluorine
• glycomimetics
• olefination
• radicals
• reduction

A new method for the synthesis of fluorinated -C-glycosides is described. The reactions between highly electrophilic radicals (fluorinated or unfluorinated) and a 2-benzyloxyglucal or galactal provide 2-keto-D-arabino- or 2-keto-D-lyxo-hexopyranosides through an addition/fragmentation process. Sodium borohydride mediated or Meerwein-Ponndorf-Verley (MPV) reduction of these compounds provides -C-glycosides that feature appropriate anchoring groups for further synthetic elaboration. The presence of CF(2)CO(2)iPr or CF2Br groups at the pseudo-anomeric position allows efficient reduction/olefination or Br/Li-exchange/nucleophilic-addition sequences. These transformations open the way for the synthesis of fluorinated C-glycosidic analogues of glycoconjugates.

• 出版日期2013-9-16