This Is AuburnElectronic Theses and Dissertations

A Cyclophane-Based Approach to [n]Cycloparaphenylenes and an Allylic Arylation Strategy for Regioselective Triphenylene Synthesis




Caroline Merryman

Type of Degree

Master's Thesis


Chemistry and Biochemistry


CHAPTER 1 Synthesis of functionalized p-terphenyl-containing macrocycles as key intermediates in the synthesis of functionalized [n]CPPs Strategically designed, substituted para-terphenyl-containing macrocycles are explored as possible key intermediates in the synthesis of functionalized [n]cycloparaphenylenes. These para-terphenyl-containing macrocycles are prepared via a streamlined synthesis, proceeding through a macrocyclic 1,4-diketone, that has been previously reported by our group. This strategy does not employ the use of cross-coupling reactions, and is, therefore, tolerant of the incorporation of the functional groups necessary to prepare [n]CPPs from these para-terphenyl-containing macrocycles. CHAPTER 2 Toward the Synthesis of [4]Cycloparaphenylene Synthetic routes towards the next smallest, yet-to-be-synthesized [4]CPP are explored. These strategies aim to employ a macrocyclic 1,4-diketone as a key intermediate. The paracyclophane-based strategy aims to bypass the challenges expected with the macrocyclization of such a highly strained molecule. CHAPTER 3 Synthesis of regioselectively functionalized triphenylenes via allylic arylation A series of unsymmetric triphenylene systems are reported. The final two steps of these syntheses are an allylic arylation onto a cyclohex-2-ene-1,4-diol-based system and subsequent aromatization. This synthetic process has been streamlined and applied to both electron rich and electron deficient systems. Selected triphenylenes are explored as substrates for further pi-extension.