This dissertation describes recent advances in methodology to access novel aromatic architectures using a benzannulation strategy (Chapter 1). Silyl protected acetylenes are readily reacted to yield the corresponding 2-naphthylsilane. These compounds serve as synthetically useful building blocks for further derivatization and iterative benzannulation to access sterically crowded substrates (Chapter 2). Despite the high efficiency of this reaction, phenylene ethynylene macrocycles prove to be too rigid to undergo complete benzannulation (Chapter 3). Finally, the scope of this transformation was expanded beyond aryl substituted acetylenes with the benzannulation of silyl-haloacetylenes (Chapter 4). These products readily generate 2-naphthynes with the addition of cesium fluoride and can be oligomerized or cyclized to isolate substituted ortho-naphthalenes. Through our fundamental studies into this transformation, we have shown it serves as a versatile reaction in the organic synthetic chemists toolbox to access novel aromatic architectures.