xiv, 326 p. : ill. (some col.) / Tetra-ortho -substituted aryl naphthalenes (TOANs) are a motif of great importance, being present in biologically active natural products, chiral ligands, and building blocks relevant to materials science. The synthesis of sterically demanding and enantioenriched TOANs continues to be a challenge for current synthetic methods. Herein, we describe the highly effective synthesis of a variety of sterically demanding and enantioenriched TOANs through a rearrangement-based method. Our method utilizes a cyclopropyl carbinol moiety as the key rearrangement precursor. We have demonstrated that carbon-carbon coupling through a simple nucleophilic attack on a cyclopropyl indanone allows for very large aryl substrates to be added and rearranged. We discuss in detail the following: 1) the initial substrate-scope and proof-of-concept studies, 2) our progress in building the most sterically demanding TOANs to date, and 3) the asymmetric synthesis of TOANs through chiral transfer. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Michael M. Haley, Chairperson; Shih-Yuan Liu, Advisor; Darren W. Johnson, Member; Victoria J. DeRose, Member; Paul J. Wallace, Outside Member