Functionalization of GlucoPyranosides at position 5 by 1,5 C-H insertion of Rh(II)-Carbenes: Dramatic influence of the anomeric configuration

Jana Hammoud; Antoine Joosten; Thomas Lecourt

doi:10.1016/j.carres.2019.107834

Functionalization of GlucoPyranosides at position 5 by 1,5 C-H insertion of Rh(II)-Carbenes: Dramatic influence of the anomeric configuration

Carbohydr Res. 2019 Dec 1:486:107834. doi: 10.1016/j.carres.2019.107834. Epub 2019 Oct 11.

Authors

Jana Hammoud¹, Antoine Joosten¹, Thomas Lecourt²

Affiliations

¹ Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA UMR 6014, 76000, Rouen, France.
² Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA UMR 6014, 76000, Rouen, France. Electronic address: [email protected].

PMID: 31689578
DOI: 10.1016/j.carres.2019.107834

Abstract

Herein, a C-H bond functionalization approach is reported as a new route towards non-natural glycosides having a quaternary position 5. The development of this transformation furthermore reveals that insertion of Rh(II)-carbenes into the C₅-H bond is controlled by remote stereoelectronic effects induced by the axial or equatorial orientation of the aglycone.

Keywords: C-H bond functionalization; Quaternarization; Rh(II)-carbene; Stereoelectronic effects.

MeSH terms

Catalysis
Electron Transport
Glycosides / chemistry*
Methane / analogs & derivatives*
Methane / chemistry
Rhodium / chemistry*
Stereoisomerism

Substances

Glycosides
carbene
Rhodium
Methane