Abstract
The thesis consists of two chapters. The first chapter describes the formal synthesis of ingenol. We used (+)-3-carene as starting material, which underwent several chemical operations to give compound 119. 1,4-Addition of compound 119 followed by iodination furnishedα-iodo ketone 152 bearing an allenic side chain. We used atom-transfer cycloaddition as the key step to construct the AC rings of ingenol. Reduction of spiro ketone 174b followed by alkylation and ring-closing metathesis reaction using catalyst 199 gave the inside-outside tetracyclic skeleton 216. Finally removal of the benzyl group followed by oxidation achieved Winkler’s intermediate 39. Thus the formal synthesis of ingenol was completed in 0.5% overall yield from (+)-3-carene in seventeen synthetic operations. The second chapter presents study of 1,3-dipolar cycloaddition of benz[de]isoquinolinium-1-ide with C60. Treatment of compound 38 with primary amines underwent retro-malonate addition reaction to generate benz[de]isoquinolinium-1-ide. Followed by 1,3-dipolar cycloaddition of benz[de]isoquinolinium-1-ide with C60 afforded the derivatives 44a-c.