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Date of Award
Thesis-ISU Access Only
Master of Science (MS)
Department of Chemistry
Timothy D. Lash
Carbaporphyrins are porphyrin analogs in which one of the pyrrole units are replaced with a carbocyclic ring. In the monocarbaporphyrinoids benziporphyrins, one of the pyrrole rings is replaced by a benzene unit. Due to cross-conjugation, benziporphyrins are not aromatic species; however, electron-donating substituents and protonation of various benziporphyrins have been shown to introduce some diatropic character into the macrocycle. Although syntheses of monocarbaporphyrins and dicarbaporphyrins have been successfully executed, to date no examples of tricarbaporphyrins or tetracarbaporphyrins have been prepared. Tetracarbaporphyrins, which have been named as quatyrins, are theoretically significant molecules that would provide insights into the aromatic characteristics of porphyrinoid systems.
In this thesis, two projects were conducted to further explore carbaporphyrin chemistry. The first project utilized a `3+1' condensation of dimethoxybenzitripyrranes with a variety of carbocyclic and heterocyclic moieties to yield novel benziporphyrin systems. These tripyrranes successfully condensed with thiophene dicarbinols to produce dimethoxythiabenziporphyrins and related palladium complexes. This `3+1' strategy was also able to produce the first examples of dibenziporphyrins. The second project targeted the synthesis of carbaporphyrinoid systems with the same carbon skeleton as quatyrin through the self-condensation of fulvene carbinols. This led to the synthesis of expanded carbaporphyrinoid systems and a dibenzodioxadicarbaporphyrin.
Fosu, Stacy, "Synthesis of Benziporphyrin Analogs and Carbaporphyrinoid Systems" (2014). Theses and Dissertations. 216.