Oxidative Activation of C–S Bonds with an Electropositive Nitrogen Promoter Enables Orthogonal Glycosylation of Alkyl over Phenyl Thioglycosides

A method for the selective activation of thioglycosides that uses the N+-thiophilic reagent O-mesitylenesulfonylhydroxylamine (MSH) as a promoter is presented. The reaction proceeds via anomeric mesitylensulfonate intermediates, which could be isolated and fully characterized by placing a fluorine a...

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Bibliographic Details
Published in:Organic letters 2017-10, Vol.19 (19), p.5490-5493
Main Authors: Kitowski, Annabel, Jiménez-Moreno, Ester, Salvadó, Míriam, Mestre, Jordi, Castillón, Sergio, Jiménez-Osés, Gonzalo, Boutureira, Omar, Bernardes, Gonçalo J. L
Format: Article
Language:English
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Summary:A method for the selective activation of thioglycosides that uses the N+-thiophilic reagent O-mesitylenesulfonylhydroxylamine (MSH) as a promoter is presented. The reaction proceeds via anomeric mesitylensulfonate intermediates, which could be isolated and fully characterized by placing a fluorine atom at the C2 position. In the presence of a soft Lewis acid, glycosylation reaction proceeds at ambient temperature with good yields. It is further demonstrated that it is possible to orthogonally activate S-ethyl in the presence of S-phenyl donors, enabling the design of sequential glycosylation strategies.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.7b02886