Chemical synthesis approaches to amphiphilic mimetic glycosides

Porter, Jack Anthony

Abstract

The majority of surfactants in use are derived from petroleum feedstocks. Synthetic surfactants face numerous issues including low biodegradability, ecotoxicity and bioaccumulation. Biosurfactants such as amphiphilic glycoconjugates are a promising candidate for the development of non-toxic, biodegradable, and sustainable alternatives. Due to the infant nature of the chemical space, structure function studies are required to fully unlock their potential and so the chemical synthesis of these materials is required.

Herein, the synthesis of pyranose-component modified oleyl based glycolipids is detailed. These modifications include fluorination at C6 and C4 within glucosides and glucosamine. Whilst pursuing galactose/galactosamine 2,3,6-tri-O/3-6-di-O-benzoates for regioselective heteroatom introduction, an understanding into the effect of anomeric aglycon and chalcogen on the outcome of low temperature regioselective protection was acquired.

A mild and reliable glycosylation method to access oleyl glucosides was developed and glycosidation of oleyl alcohol with α-trichloroacetimidate donors successfully yielded five target glycolipids. The effect of anomeric configuration and aglycon identity on regioselectivity for 2,3,6-tri-O-benzoates was also determined with α configured substrates providing complete selectivity. In the β configuration selectivity was hindered by larger and electron donating aglycons with small and electron donating aglycons favouring the 2,3,6-tri-O-benzoate. From these studies a number of advanced precursors were synthesised and effectively utilised to access further glycomimetics beyond glycolipids including glycosyl 1-phosphates. These materials provide an exciting series of tools to explore structure function relationships of amphiphilic oleyl glycoconjugates.

Citation

Porter, J. A. (2024). Chemical synthesis approaches to amphiphilic mimetic glycosides. (Thesis). Keele University. Retrieved from https://keele-repository.worktribe.com/output/849924

• Thesis Type: Thesis
• Deposit Date: Jun 13, 2024
• Publicly Available Date: Jun 20, 2024
• Public URL: https://keele-repository.worktribe.com/output/849924
• Award Date: 2024-06