Lee, Daniel2022-06-082022-06-082022-02https://hdl.handle.net/11299/227913University of Minnesota Ph.D. dissertation. 2022. Major: Chemistry. Advisor: Thomas Hoye. 1 computer file (PDF); 238 pages.Polycyclic, highly fused/conjugated aromatic organic compounds (PACs) have intrigued chemists since the discovery of naphthalene in 1821. Given the unabated interest in such molecules, the development of new methods and strategies for the practical synthesis of PACs having new structural motifs is important. The advantage of thermally generating benzynes via the cycloisomerization of a tethered tri-yne (the hexadehydro-Diels–Alder reaction) serves as an excellent platform for chemists to discover new modes of benzyne reactivities and new synthetic approaches. This thesis describes a new complementary strategy to synthesize polycyclic aromatic products from multi-ynes via the HDDA reaction. Two aspects of the application of the HDDA reaction are discussed: (1) reaction of coumarins with HDDA-benzyne, and (2) construction of structurally complex molecular architectures via radial HDDA reactions.enBenzyneCoumarinHDDAPACRadialThesis or Dissertation