Oximes and oxime ethers have found widespread use as drugs, additives, pesticides and other materials. Enzymatic metabolism of these substrates may lead to reactive intermediates such as radicals and radical ions, which may damage DNA or lead to disease. As such, a fundamental understanding of the structure and reactivity of these types of intermediates must be established. Our previous studies have shown that oxidation of oxime ethers in the presence of a nucleophile leads to nucleophilic attack at the oxidized nitrogen; therefore, oxime derivatives with built-in nucleophiles may react to give cyclized products. This pathway would generate a heterocycle, which is an important component in drug synthesis. Understanding the cyclization mechanism of oxime ethers can be used as a building block for understanding heterocycles in other molecules. Our current studies consist of oxime derivatives with carbonyls acting as the built-in nucleophile. The purpose of these studies is to 1) understand the reactive intermediates formed and involved in the photosensitized electron transfer reactions of these substrates and 2) to investigate the possible cyclization pathways of the reactive intermediates formed by photosensitization. The results of these studies will be discussed.

Heterocycle synthesis via one-electron oxidation of nucleophile-containing oxime derivatives

246th National Meeting (2013)

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