Mechanistic studies on the thermal cyclodehydrogenations of polycyclic aromatic hydrocarbons

Thesis advisor: Lawrence T. ScottThermal cyclodehydrogenation is the key step in the total synthesis of fullerene C60 and represents an important family of carbon-carbon bond-forming reactions. My research focuses on understanding the mechanism of C-C bond formation in the high temperature cyclodehydrogenations of PAHs using appropriate test cases to form 5- or 6-membered rings. My goal was to understand more about molecular reactions under extreme conditions and thereby realize new synthetic pathways for new molecules. This dissertation describes the synthesis of several substrates and studies of their thermal cyclodehydrogenations. Chapter 1 presents the cyclodehydrogenations of [5]helicene and benzo[5]helicene to form 6-membered rings under flash vacuum pyrolysis (FVP) conditions. An observed rate difference established that an electrocyclic mechanism is favored in this case and disproved the radical cyclization and 1,2-hydrogen shift/carbene insertion mechanisms. Chapter 2 describes the cyclodehydrogenations of phenyl-substituted phenanthrenes to form 6-membered rings under FVP conditions. The radical mechanism is ruled out because of the rate difference. Chapter 3 shows the synthesis of 7-(9H-fluoren-9-ylidene)-7H-benzo[c]fluorene and its thermal cyclodehydrogenation to form 6-membered rings under FVP conditions. In chapter 4, the cyclodehydrogenations of phenyl-substituted anthracenes and phenanthrenes to form 5-membered rings under FVP conditions are presented. The unexpected dominance of phenyl loss suggests that radical mechanisms are occurring during the cyclodehydrogenations. Chapter 5 describes the cyclodehydrogenations of [4]helicene and benzo[4]helicene to form 5-membered rings under FVP conditions. The results point to a carbene cyclization mechanism, in competition with the radical mechanism.Thesis (PhD) — Boston College, 2008.Submitted to: Boston College. Graduate School of Arts and Sciences.Discipline: Chemistry