Porphyrin N-Oxidations and beta,beta'-Bond Modifications

Date of Completion

January 2011


Chemistry, Organic




This thesis begins with an introduction to porphyrins and chlorins, their natural and synthetic analogues, the biological roles of porphyrins, followed by the synthesis of porphyrins and their derivatization towards chlorins. The introduction also deals with the structural analysis of porphyrins and a classification of their optical spectra, followed by a brief outline of the applications of porphyrins and chlorins. Subsequently, there is a discussion on the various types of porphyrins present with substitution in the porphyrin core as well as in the periphery. The structure, synthesis and spectroscopic properties of core substituted and peripherally modified porphyrins are also discussed.^ A detailed description of porphyrin and chlorin N-oxides is carried out in the Results and Discussion Chapter 1, describing their synthesis, reactivity, crystal structure and a comparison of their optical spectra. A possible biological application is outlined.^ An exploration of the reactivity of the porphyrin α-position and synthesis of a pyrrole-ring contracted chlorin is discussed in Chapter 2. ^ In Results and Discussion Chapter 3, the synthesis, spectroscopy and stereochemical assignment of helimeric porphyrinoids with a morpholino subunit are discussed.^ In Results and Discussion Chapter 4, the synthesis of trans-diolchlorins and their manipulation leading up to the synthesis of pyrrole ring homologated porphyrins is discussed.^