Stereoselective reactions in carbohydrate synthesis

This thesis deals with two topics connected with carbohydrate chemistry. The first part presents epoxidation and dihydroxylation reactions of glycals using Mo-catalysts and m-chloroperbenzoic acid (MCPBA) towards the synthesis of manno oligosaccharides. The oxidation of glycals afforded in all cases...

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Bibliographic Details
Author: Marín Ferré, Irene
Format: doctoral thesis
Status:Published version
Publication Date:2012
Country:España
Institution:Universitat Rovira i virgili (URV)
Repository:Repositori Institucional de la Universitat Rovira i Virgili
OAI Identifier:oai:urv.cat:TDX:1036
Online Access:https://hdl.handle.net/20.500.11797/TDX1036
http://hdl.handle.net/10803/76720
Access Level:Open access
Keyword:547 - Química orgànica
Description
Summary:This thesis deals with two topics connected with carbohydrate chemistry. The first part presents epoxidation and dihydroxylation reactions of glycals using Mo-catalysts and m-chloroperbenzoic acid (MCPBA) towards the synthesis of manno oligosaccharides. The oxidation of glycals afforded in all cases the corresponding diols or glycosides, as a consequence of the in situ opening of the epoxides initially formed. Free hydroxyl groups were observed to direct the stereoselectivity of the epoxidation, and then manno derivatives were obtained from unprotected or partially protected glucals. The results using Mo-catalysts are among the best described for the catalytic epoxidation of glycals. The results using MCPBA were excellent, and this methodology was applied to the synthesis of orthogonally protected glycosyl donors. The second part is related to the synthesis of the cardiotonic digitoxin. Two different strategies were studied in order to obtain 2-deoxy-glycosides through olefination-cyclization-glycosylation reaction and using asymmetric synthesis.