Synthesis and Functionalizations of Tetrapyrrole Derivatives

• Main Author: Jiao, Lijuan
• Other Authors: William Crowe
• Format: Others
• Language: en
• Published: LSU 2007
• Subjects: Chemistry
• Online Access: http://etd.lsu.edu/docs/available/etd-10232007-121548/

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.