Graduation Year
2010
Document Type
Dissertation
Degree
Ph.D.
Degree Granting Department
Chemistry
Major Professor
X. Peter Zhang, Ph.D.
Committee Member
Jon C. Antilla, Ph.D.
Committee Member
Roman Manetsch, Ph.D.
Committee Member
Mark L. Mclaughlin, Ph.D.
Keywords
amination, nitrene, azide, asymmetric, cyclopropanation, carbene, alzheimers, malaria, bacteria, influenza, polymer
Abstract
Porphyrins and their analogs are a class of chemically and biologically important compounds that have found a variety of applications in different fields such as catalysis, medicine, and materials. The physical, chemical, and biological dependence of the peripheral substituents of porphyrins on their properties has prompted great effort towards the synthesis of new porphyrins with different electronic, steric, and conformational environments. To this end, porphyrins have been prepared using a modular approach from bromo- and triflate synthons. These synthons underwent palladium-catalyzed cross-coupling with chiral amines, amides, alcohols, and boronic esters to create products that were tested for biological activity.
Metalloporphyrins were screened as catalysts for cyclopropanation and C-H amination, yielding excellent results. By changing the porphyrin catalysts’ chiral groups, all four enantiomers could be produced in the cyclopropanation of styrene derivatives with ethyl diazoacetate (or t-butyl diazoacetate). Similarly, a variety of sultams were produced from benzenesulfonyl azides in high yields and high enantioselectivities using chiral cobalt porphyrins as catalysts.
Porphyrins, metalloporphyrins, and the catalytic products generated were tested for activity in a variety of medicinal collaborations, namely as therapeutics for methicillin-resistant Staphylococcus aureus, Alzheimer’s disease, malaria, viral infections that include influenza and herpes, and cancer, as well as biological studies with ferrochelatase. They were also used in materials experiments with two different polymer groups.
Scholar Commons Citation
Fields, Kimberly Bliss, "The Design and Synthesis of Functionalized Porphyrins and Their Applications in Group Transfer Reactions, Medicine, and Materials" (2010). USF Tampa Graduate Theses and Dissertations.
https://digitalcommons.usf.edu/etd/3461
