The formation of medium-sized nitrogen heterocycles from the annulation reactions of allylic silanes

Nitrogen-containing ring systems are common structural motifs in naturally occurring organic molecules. Since many natural products exhibit potent biological activity, synthetic methods for the formation of nitrogen heterocycles have valuable applications in the pharmaceutical sciences. Despite their importance in organic synthesis, there are few methods for the diastereoselective formation of medium-sized nitrogen heterocycles. This thesis describes the formation of medium-sized nitrogen heterocycles through the cycloaddition reactions of allylic silanes. Chapter 1 provides the current methods for the formation of five-membered ring nitrogen heterocycles, and brings to light the limited methods for medium-sized ring formation. Chapter 2 describes the efforts towards the [3+3] cycloaddition of an allylic silane and an aziridine. Chapter 3 details the formation of medium-sized lactams through the translactamization of nitrogen-tethered gamma-lactams. Several methods for the formation of nitrogen tethered gamma-lactams are investigated, and six-, seven-, and eight-membered ring lactams are formed by translactamization. Chapter 4 describes the employment of the methodology established in Chapter 3 towards the synthesis of the pseudodistomin alkaloids.