Doctor of Philosophy (PhD)
This Dissertation is divided into five chapters reporting various aspects of the background to my field of study and the results obtained during my research program. Chapter 1 gives a very brief introduction to photodynamic therapy including the mechanism of the treatment, the localization of photosensitizer in tumor cells, the pathways leading to tumor death and characteristics of various photosensitizers such as porphyrin-based photosensitizers and non-porphyrin based photosensitizers. Chapter 2 reports a total synthesis of zinc(II) isoporphyrins by cyclization of b-bilene salt using á-keto esters for the macrocyclization carbon. Functionalization of the resulting zinc(II) isoporphyrins was attempted using different strategies such as direct functionalization of the isoporphyrin after cyclization of the b-bilene salt and introduction of the functional group during the cyclization of b-bilene salt. Chapter 3 desrcibes a different total synthesis of zinc(II) isoporphyrins by way of the MacDonald 2+2 condensation approach. A serial of zinc(II) isoporphyrins were obtained and further functionalization of these compounds was also attempted by use of various hydrolytic reactions. Functionalization of dipyrromethanes before cyclization was also investigated through hydrolytic and amination reactions. Chapter 4 explores novel syntheses of BODIPYs using pyrroketones as starting materials. Reactions of pyrroketoned including electropholic alkylation with Meerwein’s salt, chlorination using phosgene, and protonation with acids were investigated. The reactivity of the derivatives, especially, 5-chloro-dipyrromethenes and 8-chloro-BODIPYs were also investigated by using replacement (substitution/elimination) and modern organometallic coupling reactions. Some meso-substituted BODIPYs were obtained and their photophysical properties were studied, including absorption, fluorescence and quantum yields. Chapter 5 presents a synthesis of tri-chloro-BODIPYs. Global and regioselective Stille coupling reactions were investigated using tri-chloro-BODIPYs. A novel series of new symmetrical and unsymmetrical BODIPYs s were synthesized using this method.
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Wang, Haijun, "Syntheses and characterization of isoporphyrins and BODIPYs for PDT and imaging" (2014). LSU Doctoral Dissertations. 2815.