Open Collections

Syntheses of affinity ligands and monoazaporphyrins

University of British Columbia

Heme and heme proteins are ubiquitous in nature and play many varied and important biological functions. The biological properties of the heme proteins are dependent on the interaction between the metal and the porphyrin where each is dependent on the other to carry out specific functions. This thesis describes the syntheses of affinity ligands and monoazaporphyrins. The synthesis of the ligand was based on a protoporphyr in-IX derivative substituted on either the 2- or 4-vinyl group. The two isomeric affinity ligands, 73 and 74 (2- or 4- substituted) were synthesized from protoporphyrin-IX di-tert-butyl ester 106b by conversion of the vinyl groups to monoformyl derivatives 122b (or 123b) via the intermediacy of photoprotoporphyrin-IX derivatives. The spacer chain [formula omitted] using a formyl group was extended by Knoevenagel condensation with malonic acid to give monoacrylic acid derivatives 132 (or 133). This chain was further extended by linking an aliphatic diamine (1,3-diaminopropane) to the monoacrylic acid derivatives 132 (or 133) through an acid chloride mediated amide linkage. The Fe(III) and Co(II) complexes of the affinity ligand (73 + 74) were prepared and the tertiary butyl groups were removed by treatment with trifluoroacetic acid at room temperature to give 71 and 72. [formula omitted] An improved synthesis of monoazaporphyrins (5-aza) (see p.iv) is described in this work (section 3.4). Our approach consists of constructing 1,19-dibromo-l,19-dideoxybiladiene-ac dihydrobromides which were subsequently cyclized, to give corresponding monoazaporphyrins in high yields, using dibenzo-18-crown-6 as a phase transfer agent for the transfer of an azide ion. [formula omitted]

Text

2012-03-15

For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.

http://hdl.handle.net/2429/41441

Chemistry

University of British Columbia

Graduate