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

被引：28
作者：
Colombel, Sophie [1 ,2 ]
Van Hijfte, Nathalie [1 ,2 ]
Poisson, Thomas [1 ,2 ]
Leclerc, Eric [3 ]
Pannecoucke, Xavier [1 ,2 ]
机构：
[1] Normandie Univ, COBRA, UMR 6014, F-76821 Mont St Aignan, France
[2] Univ Rouen, FR 3038, F-76821 Mont St Aignan, France
[3] UMR 5253 CNRS UM2 UM1 ENSCM 8, Inst Charles Gerhardt, F-34296 Montpellier 5, France
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 38期
关键词：
fluorine; glycomimetics; olefination; radicals; reduction; ORGANOFLUORINE-ORGANOSILICON CHEMISTRY; DIFLUOROMETHYL RADICALS; PHOSPHOTYROSYL MIMETICS; GLYCALS; ANALOGS; GALACTOSYLCERAMIDES; GLYCOPEPTIDE; SUBSTITUTION; GENERATION; REDUCTIONS;
D O I：
10.1002/chem.201302070
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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.
引用
收藏
页码：12778 / 12787
页数：10
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