Pyrrole-containing alkaloids have long captured the attention of the synthetic chemistrycommunity due to their intriguing and reactive chemical architectures; such is the case of curvulamine and associated polypyrrole natural products. Curvulamine, curindolizine, and the related bipolamines share a unique compact pentacyclic skeleton flanked by two electron-rich pyrroles and up to seven stereocenters. Synthetic access to these complex alkaloids has previously been limited to curvulamine and bipolamine I. In this work, we aim to chronicle the results of our synthetic investigations into this family of unique alkaloids. In the first chapter, we provide an overview into their isolation and antibiotic properties, and discuss our initial synthesis of curvulamine which frames our studies in subsequent chapters. The second chapter describes the total synthesis of curindolizine and the substrate scope of a microwave-assisted method to access pyrroloazepinones, bicyclic heterocycles used in the synthesis of curvulamine and curindolizine. Finally, in the last chapter we describe the synthetic strategies used to access bipolamine C, D, G, and I and describe the unexpected reactivity of some pyrrole-containing intermediates along this journey.