Conversion of Glycals to 2,3-Di-Substituted-3-Deoxy-Glycals by N-(Glycosyloxy) Acetamides-assisted C-2-Alkenylation and C-3-Nucleophilic Substitution

Chem Asian J. 2022 Jul 15;17(14):e202200350. doi: 10.1002/asia.202200350. Epub 2022 May 23.

Abstract

Transformation of glycals to 2,3-di-substituted-3-dexoy-glycals were achieved by sequential C2 alkenylation of pseudoglycals followed by capture of nucleophiles at C3 position. Anomeric linked N-(glycosyloxy) acetamides group assisted innate C2-H activation of pseudoglycals under palladium catalysis is achieved. The synthesized C2 alkenylated products were further attacked by thio/amino nucleophiles at C3 position under basic conditions in stereo-selective fashion to generate 2,3-branched glycals with the elimination of directing groups and translocation of double bond. Different control experiments were conducted to establish the role of directing groups in C-H functionalization of pseudoglycals and reason for selectivity.

Keywords: 2,3-di-substituted-3-dexoy-glycals; C−H activation; amino sugar; directing group; pseudoglycals; thiosugar.

MeSH terms

  • Acetamides*
  • Catalysis
  • Palladium* / chemistry

Substances

  • Acetamides
  • Palladium