Year of Award

2016

Document Type

Dissertation

Degree Type

Doctor of Philosophy (PhD)

Degree Name

Chemistry (Organic Option)

Department or School/College

Department of Chemistry and Biochemistry

Committee Chair

Nigel Priestley

Commitee Members

Orion Berryman, Kent Sugden, Christopher Palmer, Stephen Lodmell

Keywords

DNMT1, inhibitor, methylation

Abstract

The acquisition of genomic alterations is a defining feature of human cancers. Many cancer chemotherapies rely upon an apoptotic pathway to eradicate cells containing those alterations. One such alteration is the epigenetic methylation of cytosine in DNA, which occurs at CpG sites in dense clusters of CpG dinucleotide repeats within the gene promoter region. The maintenance of appropriate methylation levels of DNA is necessary during normal DNA replication. Disruption of correct and appropriate methylation patterns leads to DNA associated with transcriptional silencing. Cytosine methylation is catalyzed by DNA methyltransferase enzymes (DNMTs), which transfer a methyl group from S-adenosylmethionine to the 5-position of cytosine to yield 5-methylcytosine. While there are four main classes of DNMTs, DNMT1 is the most abundant methylase responsible for maintaining gene expression patterns following cell division. Therapeutics that can inhibit DNMT1 can reactivate genes silenced by hypermethylation, therefore, the design and development of novel DNMT1 inhibitors is a worthy goal, especially since the silenced genes remain intact and functional. This dissertation outlines a systematic approach taken to the successful design and testing of isoindolinone-based DNMT1 inhibitors. Three synthetic routes were employed to create the inhibitors, the routes include an Ugi-IMDAF reaction, a multiple step scheme using homothallic acid as a starting point, and utilizing convertible isocyanides. The best compound synthesized and tested was 78, which has a % DNMT1 activity of 7.31 ▒ 0.98 and a calculated KiÆ value of 18 ▒ 3 ╡M.

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© Copyright 2016 Patrick Anthony Barney