Synthesis Of Oligosaccharide Mimetics By The Desulfurative Rearrangement Of Allylic Disulfides And Stereoelectronic Influence Of C-O Bonds On C- And O-Glycosylation

SYNTHESIS OF OLIGOSACCHARIDE MIMETICS BY THE DESULFURATIVEREARRANGEMENT OF ALLYLIC DISULFIDES AND STEREOELECTRONICINFLUENCE OF C-O BONDS ON CAND O-GLYCOSYLATIONbyMYRIAME MOUME-PYMBOCKMay 2013Advisor:Dr David CrichMajor:ChemistryDegree:Doctor of PhilosophyThis dissertation focuses on two different problems. The first part of thismanuscript presents the application of a novel methodology to access thesynthesis of oligosaccharide mimetics while the second part focuses on the studyof the stereoelectronic effects of proximal C-O bonds in Cand O-glycosylationreactions.The first chapter provides a brief overview of the important roles thatoligosaccharides and glycoconjugates play in biological processes and sets outthe major advances that have been made in the past few decades in thesynthesis of such complex structures while bringing out the ongoing challengesand the limitations that impede the development of general methods with broadapplicability.In chapter two, the emphasis is placed on a new thioligation reactiondeveloped in the Crich laboratory as a means for the chemical synthesis of linearmimetics of an important bacterial motif, the β-(1→6)-N-acetyl glucosamine