Stereospecific synthesis of a DL-gala-aminoquercitol derivative

Abstract

A new aminoquercitol derivative was synthesized starting from 1,4-cyclohexadiene. Photooxygenation of cyclohexa-1,4-diene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxicle as the main product. The formed hydroperoxy endoperoxide was reduced with LiAlH(4) to produce anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol. Protection of alcohol with acetyl chloride followed by reduction of the endoperoxide with thiourea, and then palladium-catalyzed ionization/cyclization reaction gave an oxazolidinone derivative. Hydrolysis of the oxazolidinone ring and acetylation gave an amino compound. Oxidation of the double bond in the amino compound with OsO(4) followed by acetylation gave the amino tetraacetate and removal of the acetate groups furnished the desired aminoquercitol whose exact configuration was determined by X-ray diffraction analysis. (C) 2010 Elsevier Ltd. All rights reserved.