Stereospecific synthesis of a new class of aminocyclitol with the conduramine D-2 configuration

Abstract

A new aminocyclitol derived from bicyclo[4.2.01,6]octane was synthesized starting from cyclooctatetraene. Photooxygenation of trans-7,8-diacetoxy-bicyclo[4.2.0]octa-2,4-diene afforded a bicyclic endoperoxide. Reduction of the endoperoxide with thiourea followed by a palladium-catalyzed ionization/cyclization reaction gave an oxazolidinone derivative. Oxidation of the double bond in the oxazolidinone with KMnO4 followed by acetylation gave the oxazolidinone-tetraacetate whose exact configuration was determined by X-ray diffraction analysis. Hydrolysis of the oxazolidinone ring and removal of the acetate groups furnished the desired aminocyclitol.