The Hexadehydro-Diels-Alder Reaction
Most of the work in the Hoye labs involves investigations of the HDDA (hexadehydro-Diels-Alder) reaction. Their initial findings were published in the journal Nature in 2012. As they continue to discover new types of chemical transformations involving the HDDA reaction, they rely on the aid of computational chemistry to help explain results and guide them in future directions. They have recently been discovering new reactions of HDDA-generated arynes with various traps. Examples include (but are not limited to) ene-reactions, reactions with carbonyl compounds, and intramolecular reactions with alkanes to give C-H insertion products. As the group continues to learn more about these reactions, computations will both offer mechanistic insight to these reactions and indicate to us the types of substrates may act as more effective traps.
In conjunction with the Center for Sustainable Polymers, these researchers are currently investigating a broad range of sustainable monomers that will engage in ROP (Ring-Opening Polymerization) processes to evaluate new polymeric materials with unique properties. Typically, these lactones and lactams are derived from natural, renewable resources, and display a variety of functionalization and substitution on the cyclic monomer core. MSI resources are used to compute the energetics of new classes of monomeric substrates via an isodesmic reaction model. The data obtained can then be assessed against experimentally determined thermodynamic and entropic values (typically with linear regression analysis), and ultimately developed into a model system that can forecast suitable reaction temperature and concentration for the polymerization of novel monomer systems.
The researchers have also taken advantage of computational chemistry to assist in structural elucidation. They often synthesize isomers that are difficult to differentiate from each other through conventional spectroscopic experiments. In these cases, they can compute the NMR chemical shifts in order to determine the structure. Specifically, they calculate the chemical shifts for several candidate structures and see which one mostly closely matches the experimental data. This has proven useful on many occasions.
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