Synthesis of (2-deoxy-α- d-glyc-2-enopyranosyl)arenes by stereospecific counjugate-addition of organocopper reagents to peracetylated hex-1-enopyran-3-uloses

Abstract

The reaction of peracetylated 1,5-anhydro-2-deoxyhex-1-eno-3-uloses with higher-order cyanoorganocuprate in oxolane at low temperature in the presence of acetic anhydride afforded the corresponding glycosylarenes in good yields. A complete stereocontrol could be achieved, leading to the α- d anomer without epimerization at C-4.The configuration of the new products was established by spectroscopic methods and transformation into the crystalline parent oximes, the conformation of which is discussed in terms of stereoelectronic effects.