The Diels-Alder (DA) reaction is among the most important and versatile methods in creating ring molecules, and factors governing stereoselectivity and rate have been widely studied. However, the chemoselectivity in products are often restricted, as electronic natures of the reactants (typically electron-rich diene and electron-poor dienophile) have to be matched.<br/><br/>On the other hand, in radical chemistry, the removal of a free election helps promote an entirely different chemical environment within the reactants. This is experimentally shown to be imperative in forming a different set of products not predicted in neutral DA reactions using photochemistry or redox chemistry. Using an emerging technique known as quasi-classical dynamics, coupled with Density Functional Theory, we investigated the radical cation DA reactions of anethole with isoprene and cyclopentadiene to provide quantitative understanding to this observed phenomena. We also aim to demonstrate the applicability of this understanding in reactions where minor products are actually desired. This has never been applied to the study of radical cycloadditions before.

Understanding stereoselectivity in radical cation Diels-Alder reactions using quasi-classical dynamics

2019 Spring National Meeting

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