Open Access Te Herenga Waka-Victoria University of Wellington
thesis_access.pdf (30.31 MB)

Approaches to the Synthesis of Glycosides

Download (30.31 MB)
posted on 2021-11-05, 02:53 authored by Furneaux, Richard Hubert

In a search for better synthetic routes to O- and S-glycosides, a number of mercury(II) containing derivatives of 1-thio-D-glucose were synthesised, and their reactions with thiols and acids were investigated as well as their pyrolytic behaviour. A new route to O-acetylated glycosyl thiols involving specific S-deacetylation of peracetylated 1-thioglycoses was developed by the conversion of 1-thio-Beta-D-glucopyranose pentaacetate into tetra-O-acetyl-1-S-phenylmercury (II) thio-Beta-D-glucopyranose and subsequent demercuration of this by hydrogen sulphide. A range of acylated alkyl and aryl 1,2-trans-1-thioglycosides was prepared by one step processes from peracylated 1,2-trans-related sugars by a procedure which involved the use of equimolar proportions of thiols together with boron trifluoride. A similar procedure was used to obtain benzoylated 1,2-cis-O-glucosides from penta-O-benzoyl-Beta-D-glucopyranose. Partial desulphurisation of acetylated glucosyl phenyl disulphide with tris(diethylamino)phosphine led to both phenyl tetra-O-acetyl-1-thio-alpha-D-glucopyranoside and the alpha, beta-linked thiotrehalose peracetate. Phenyl 1-thiohex-1-enopyranosid-3-ulose esters were obtained from the light induced reactions of N-bromosuccinimide with acetylated and benzoylated phenyl 1-thiogluco- and galacto-pyranosides; the acetylated 1-thioglycosides gave mixtures of 2-O-acetyl and 2-O-monobromoacetyl 1-enosid-3-uloses. Methyl hexuronate derivatives were brominated alpha to the carbonyl function by N-bromosuccinimide, and a new synthetic route to L-ascorbic acid has been proposed following the successful bromination of methyl tri-O-acetyl-2,6-anhydro-L-gulonate.


Copyright Date


Date of Award



Te Herenga Waka—Victoria University of Wellington

Rights License

Author Retains Copyright

Degree Discipline


Degree Grantor

Te Herenga Waka—Victoria University of Wellington

Degree Level


Degree Name

Doctor of Philosophy

Victoria University of Wellington Item Type

Awarded Doctoral Thesis



Victoria University of Wellington School

School of Chemical and Physical Sciences


Ferrier, R J