Here we described our use of computational chemistry to investigate the overall scope of an oxime ether radical cation intramolecular cyclization pathway towards heterocycles. Heterocycles are a reoccurring structure in organic chemistry and are commonly found in pharmaceuticals, pesticides and dyes.  One common way to synthesize heterocycles involves the cyclization of oximes or oxime ethers using either transition metal catalysts or strong acids. Recent experimental work in the de Lijser laboratory at California State University, Fullerton has concentrated on developing a more environmentally friendly approach using photo-induced electron transfer (PET) to produce oxime ether radical cation reactive intermediates that subsequently undergo intramolecular cyclization. This is a greener synthetic route as the reaction only requires light and an organic catalyst. Previous work has focused on the PET-induced cyclization of oxime ethers containing built-in aryl, thiophene, or furan groups.<br/>In this poster, we describe our efforts to predict the feasibility of the PET-induced cyclization of benzaldehyde oxime ethers that contain a built-in azole group.  Specifically, we use modern density functional theory approaches, ωB97M-V/def2-QZVPP//ωB97X-D/cc-pvdz, to understand how the formation and reactivity of the oxime ether radical cation is affected by the specific identify of the built-in azole nucleophile.  We additionally examine the extent to which the thermodynamics and kinetics of radical cation formation through PET is tunable through substituents on the central benzene ring.  As a whole, the presented work provides insights into the overall scope of this photoredox approach towards synthesizing complex heterocycles.

Computational studies of the formation of complex heterocycles through the cyclization of benzaldehyde oxime ethers containing a built-in azole group

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.