Thesis advisor: Peter X. Zhang / Thesis advisor: James P. Morken / Radical reactions have attracted continuous research interest in recent year considering their diverse reactivities. Hydrogen-atom abstraction (HAA), as one type of the most well-explored radical reactions, has been identified as one of powerful tools for C–H functionalization. Reactions involving 1,4-HAA, which is typically a challenging process both entropically and enthalpically, are rather scarce, while 1,5-HAA have been well demonstrated for variety of synthetic applications. Guided by the concept of metalloradical catalysis (MRC), 1,4-HAA was for the first time utilized as the key step to achieve asymmetric construction of chiral ring structures: cyclobutanones, azetidines and tetrahydropyridines. The design of different D2-symmetric chiral amidoporphyrin as the supporting ligand is the key to all these transformations. The reactions can be conducted under mild conditions, affording corresponding ring structure in good yields with excellent selectivity. Furthermore, The combined computational and experimental studies have shed light on the mechanistic details of these new asymmetric radical intramolecular C–H alkylation processes, which are fundamentally different from existing catalytic systems involving metallocarbenes for concerted C–H insertion. We envision that these asymmetric radical processes via Co(II)-based MRC could become an alternative method for important chiral ring structures synthesis and potentially provide new opportunities for complex molecule construction. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.