Identifier

etd-10232007-121548

Degree

Doctor of Philosophy (PhD)

Department

Chemistry

Document Type

Dissertation

Abstract

Chapter 1 of this Dissertation presents a brief overview of the history of tetrapyrrole derivatives and of their fundamental properties. Overviews of porphyrins, benzoporphyrins, chlorins and porphycenes are presented. Work presented in Chapter 2 through Chapter 4 mainly focuses on the syntheses and functionalization of chromophore-extended porphyrin derivatives. Several new synthetic routes for the syntheses and functionalizations of extended porphyrins either at the β-position or at the meso-position of porphyrin are developed. From these improved synthetic routes, the regio-selective syntheses of porphyrin derivatives are described. Chapter 2 mainly focuses on the syntheses of β,β'-fused methylenepropanoporphyrins and related porphyrin dimers. Chapter 3 mainly describes a new synthetic route for selective synthesis of benzoporphyrin regioisomers and Chapter 4 mainly discusses new work on the efficient synthesis of the so-called "Hangman Porphyrin" analogs. Chapter 5 consists two parts. The first part is devoted results of work on the total synthesis of an important porphycene derivative, 9-capronyl-oxytetrakis(methyoxyethyl)-porphycene, which has already been shown to have attractive potential applications in photodynamic therapy of tumors. The second part of Chapter 5 concerns the improved syntheses of 2,2'-bipyrrole, which is an important part of our effort to improve the synthesis of porphycene and related tetrapyrrole derivatives. The potential utility of these 2,2'-bipyrroles as bio-probes and ion-binding reagents are also tested. Chapter 6 reports mechanistic studies on the unique regio-selective formation of mono-(L)-aspartylchlorin-e6. This important photodynamic therapy (PDT) photosensitizer has recently undergone a structural revision, and the work reported in this Chapter provides a rationale for the formation of the unexpected regioisomeric structure now known to belong to mono-(L)-aspartylchlorin-e6.

Date

2007

Document Availability at the Time of Submission

Release the entire work immediately for access worldwide.

Committee Chair

Kevin M. Smith

DOI

10.31390/gradschool_dissertations.1309

Included in

Chemistry Commons

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