Thesis advisor: Shih-Yuan Liu / Described herein are two projects on the application and effects of BN/CC isosterism on indole-containing compounds. In the first chapter, the synthetic route to an unnatural boron and nitrogen-containing analogue of tryptophan (BN-tryptophan) via late-stage functionalization of BN-indole is disclosed and its spectroscopic properties are reported with respect to the natural amino acid, tryptophan. The incorporation of BN-tryptophan into proteins expressed in E. coli using selective pressure incorporation, a residue specific method of unnatural amino acid incorporation, is then reported and its reactivity and fluorescence in the proteins characterized. In the second chapter, the synthesis of a BN-indole-containing aromatic scaffold is reported and the cation-π binding ability characterized by nuclear magnetic resonance (NMR) monitored titrations is disclosed. The resulting chemical shifts were analyzed using a non-linear curve fitting procedure and the extracted association constants (Ka’s) compared with the natural indole scaffold. Computations were also performed to support the titration results. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

xxv, 468 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / 1,2-Dihydro-1,2-azaborine is a six-membered aromatic heterocycle that is related to the quintessential aromatic molecule, benzene, via the replacement of a CC fragment in benzene with an isoelectronic BN bond-pair. Like the benzene motif, 1,2-dihydro-1,2-azaborine derivatives could provide opportunities in fields ranging from medicine to materials. Recent breakthroughs in the synthesis of 1,2-dihydro-1,2-azaborine have led to a burgeoning interest in this relatively unexplored heterocycle. This dissertation describes the synthesis, characterization, and potential applications of novel 1,2-dihydro1,2-azaborines. Chapter I reviews the chemistry of monocyclic and polycyclic BN-heterocycles over the last fifty years. Chapter II introduces the synthesis of numerous boron-substituted 1,2-dihydro-1,2-azaborine derivatives from a versatile precursor. Chapter III discusses the first successful synthesis of the parent 1,2-dihydro-1,2-azaborine, which is isoelectronic with benzene itself. An examination of the chemistry of 1,2-dihydro-1,2-azaborine provides a direct comparison of its properties relative to benzene. Chapter IV discusses the synthesis and characterization of 1,2-dihydro-1,2-azaborines incorporated into phenylacetylenic scaffolds. Chapter V discusses unrelated work on nitrated lipids, which was performed under the guidance of Professor Bruce Branchaud. The chapter introduces the importance of nitrated lipids in a biological context and details the synthetic achievements in this field. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Michael Haley, Chairperson, Chemistry; Shih-Yuan Liu, Advisor, Chemistry; David Tyler, Member, Chemistry; Raghuveer Parthasarathy, Outside Member, Physics