Synthesis 2012; 44(24): 3731-3734
DOI: 10.1055/s-0032-1317013
practical synthetic procedures
© Georg Thieme Verlag Stuttgart · New York

Gram-Scale Quaternarization of the Anomeric Position of Carbohydrates: Dramatic Effects of Molecular Sieves on Rhodium(II)-Mediated Decomposi­tion of Diazo Sugars

Mélissa Boultadakis-Arapinis
Laboratoire de Chimie Thérapeutique (UMR CNRS 8638), Université Paris Descartes, Sorbonne Paris Cité, Faculté des Sciences Pharma­ceutiques et Biologiques, 4 avenue de l’Observatoire, 75006 Paris, France, Fax: +33(1)43291403   Email: [email protected]
,
Camille Lescot
Laboratoire de Chimie Thérapeutique (UMR CNRS 8638), Université Paris Descartes, Sorbonne Paris Cité, Faculté des Sciences Pharma­ceutiques et Biologiques, 4 avenue de l’Observatoire, 75006 Paris, France, Fax: +33(1)43291403   Email: [email protected]
,
Laurent Micouin
Laboratoire de Chimie Thérapeutique (UMR CNRS 8638), Université Paris Descartes, Sorbonne Paris Cité, Faculté des Sciences Pharma­ceutiques et Biologiques, 4 avenue de l’Observatoire, 75006 Paris, France, Fax: +33(1)43291403   Email: [email protected]
,
Thomas Lecourt*
Laboratoire de Chimie Thérapeutique (UMR CNRS 8638), Université Paris Descartes, Sorbonne Paris Cité, Faculté des Sciences Pharma­ceutiques et Biologiques, 4 avenue de l’Observatoire, 75006 Paris, France, Fax: +33(1)43291403   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 21 May 2012

Accepted after revision: 10 July 2012

Publication Date:
29 August 2012 (online)


Abstract

The optimization of rhodium(II) carbene mediated quaternarization of the anomeric position of carbohydrates is reported. Preparation of ketopyranosides in good and reliable yields requires reverse addition of the substrate to a highly diluted suspension of the catalyst in refluxing 1,2-dichloroethane, as well as addition of a carefully controlled amount of molecular sieves, and vigorous stirring. Following these optimized reaction conditions, functionalization of the anomeric position of carbohydrates can finally be performed on a preparative scale.

Supporting Information

 
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