Glycosylamine derivatives are biologically relevant compounds widespread in Nature, but the synthesis of this motif has been little addressed and its access with control of configuration at the anomeric carbon is challenging. Glycals substituted at C-3 with a carbamate group undergo, upon dehydration, a prompt allyl cyanate to isocyanate rearrangement to the isomeric Nglycosyl isocyanates, which can be conveniently trapped by one-pot nucleophilic addition with alcohols or amines to afford N-glycosyl carbamates and ureas, respectively. The rearrangement follows a [3,3]-sigmatropic pericyclic mechanism as illustrated by the stereospecificity of the reaction, with nitrogen being delivered at the anomeric position to the same face from which the oxygen at C-3 has departed. Thus, glucal and galactal give β-N-glycosides exclusively while allal furnishes α-N-glycosides. cis-Dihydroxylation of the synthesized unsaturated Nglycosides afford different 1-aminosugars with good selectivity

Stereospecific access to α- and β-N-glycosylamine derivatives by a metal free O-to-N [3,3]-sigmatropic rearrangement / Debora Pratesi, Stefania Mirabella, Giulia Petrucci, Camilla Matassini, Cristina Faggi, Francesca Cardona, Andrea Goti. - In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1099-0690. - STAMPA. - 2022:(2022), pp. 1-8. [10.1002/ejoc.202200804]

Stereospecific access to α- and β-N-glycosylamine derivatives by a metal free O-to-N [3,3]-sigmatropic rearrangement

Debora Pratesi;Stefania Mirabella;Camilla Matassini;Cristina Faggi;Francesca Cardona;Andrea Goti
2022

Abstract

Glycosylamine derivatives are biologically relevant compounds widespread in Nature, but the synthesis of this motif has been little addressed and its access with control of configuration at the anomeric carbon is challenging. Glycals substituted at C-3 with a carbamate group undergo, upon dehydration, a prompt allyl cyanate to isocyanate rearrangement to the isomeric Nglycosyl isocyanates, which can be conveniently trapped by one-pot nucleophilic addition with alcohols or amines to afford N-glycosyl carbamates and ureas, respectively. The rearrangement follows a [3,3]-sigmatropic pericyclic mechanism as illustrated by the stereospecificity of the reaction, with nitrogen being delivered at the anomeric position to the same face from which the oxygen at C-3 has departed. Thus, glucal and galactal give β-N-glycosides exclusively while allal furnishes α-N-glycosides. cis-Dihydroxylation of the synthesized unsaturated Nglycosides afford different 1-aminosugars with good selectivity
2022
2022
1
8
Goal 3: Good health and well-being
Debora Pratesi, Stefania Mirabella, Giulia Petrucci, Camilla Matassini, Cristina Faggi, Francesca Cardona, Andrea Goti
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/1288234
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