O’Doherty group has been working to bring the principles of asymmetric catalysis to the area of oligosaccharide synthesis. Over the years, the hexoses and related monosaccharides have served as excellent target molecules to text the synthetic viability of new asymmetric methods. While these efforts have proven utility in the arenas of carbohydrate based natural product total synthesis and carbohydrate medicinal chemistry, there has been a paucity of application of these approaches to oligosaccharide synthesis. To address this need, we have developed an alternative asymmetric approach to oligosaccharide synthesis. This approach revolves around the use of asymmetric catalysis for the synthesis of optically pure furan alcohols and the Achmatowicz oxidative rearrangement for their conversion into four stereoisomeric pyranones. These pyranones intermediates, in turn, can be converted into various monosaccharide pyranoses. Unique to this approach is the fact that these pyranones can also be oligomerized by a Pd(0)-catalyzed glycosylation reaction and in analogous fashion, these oligo-pyranone products can be converted into oligosaccharides. We have found this approach to be quite powerful. More recently, we have found a Pd/B-duel catalysis system that significantly expands the range of structural motifs that can be addressed by this asymmetric Achmatowicz approach. Herein, we update our synthetic efforts aimed at exploring the application of this methodology in oligosaccharide synthesis and related medicinal chemistry studies.

De Novo Synthesis of oligosaccharide via bi-metallic catalysis

253rd National Meeting (2017)

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