Syntheses and transformations of novel nitrogen and sulfur containing morphinanedienes

摘要

The synthesis of 6-azido-6-demethoxythebaine (10) has been performed starting from thebaine (1). Compound 10 undergoes a cycloaddition reaction with the azadienophile PTAD to form bridgehead azide 14. The acid catalyzed rearrangement of isothiocyanato diene 11 obtained from azido diene 10 and thiocyanato dienes 8 and 9 leads to sulfur containing derivatives of apocodeine (17-20).