Wang, Shengyang2020-02-262020-02-262019-12https://hdl.handle.net/11299/211816University of Minnesota Ph.D. dissertation. December 2019. Major: Chemistry. Advisor: Christopher Douglas. 1 computer file (PDF); xii, 402 pages + 1 supplementary file.This thesis is composed of two parts: in Chapter 1, 2 and 3, the development of transition metals/Lewis acids co-catalyzed aminocyanation of unsaturated C‒C bonds via N‒CN bond activation was described and discussed. In Chapter 4 and 5, a new synthetic route to cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs) was explored, followed by the studies on optical and electrochemical properties of synthesized rubicene derivatives. Chapter 1 briefly introduces catalytic difunctionalization of unsaturated C‒C bonds via addition reactions and cyanofunctionalization of multiple bonds via C‒CN bond activation. Chapter 2 and 3 describe our recent reported intramolecular aminocyanation of alkenes via N‒CN bond activation by palladium/Lewis acid cooperative catalysis, and an ongoing project: intermolecular aminocyanation of unsaturated C‒C bonds via N‒CN bond activation, in order to readily prepare heterocycles with quaternary centers and regioselective β-amino acids. Chapter 4 summarizes the physical properties and synthetic methods of CP-PAHs, as well as rubicene, as a member of CP-PAHs. Chapter 5 concludes our recent work on development of a new synthetic route to naphtho[2,3-a]aceanthrylenes and dibenzo[g,s]rubicenes, using a tandem Sonogashira cross-coupling and tetra-dehydro-Diels−Alder cycloaddition cascade, which provides a facile fine-tuning method for the optical and electrochemical properties of potential electron acceptors.enAminocyanationcyclopenta-fused polycyclic aromatic hydrocarbonsN‒CN bond activationRubicenetetra-dehydro-Diels−AlderThesis or Dissertation