Asymmetric epoxidation of unfunctionalised alkenes catalysed by d-fructose derivatives

Identifier:  TDX:1291

Handle: https://hdl.handle.net/20.500.11797/TDX1291

Authors:  Nieto Alonso, Natalia

Abstract:
In this thesis we focus on the synthesis of enantiopure epoxides using D-fructose derivatives as catalysts. A practical synthesis of the previously reported Shi’s diester catalyst (4,5-Di-O-acetyl-1,2-O-isopropylidene-D-erythro--2,3-hexadiulo-2,6-pyrano-se) was developed. Synthetic aspects such as selectivity, efficiency, cost and environmental issues of the reagents were taken into account. Optimisation of the work-up allowed for the isolation of its dihydrate derivative (no described previously). The epoxidation conditions using both D-fructose derivatives (diester and its hydrate) were optimised. Both catalysts were subsequently assayed in the asymmetric epoxidation of an array of unfunctionalised alkenes obtaining high activities and enantioselectivities. Finally, labelling experiments provided a sound understanding of the stereoinduction processes.