Professor Thomas Hoye

CSENG Chemistry
College of Science & Engineering
Twin Cities
Project Title: 
The Hexadehydro and Pentadehydro-Diels-Alder Reaction

Research in the Hoye labs often involves investigations of the hexadehydro-Diels-Alder (HDDA) reaction. Their initial findings were published in the journal Nature in 2012. They continue to discover new types of chemical transformations surrounding this reaction. To better understand underlying reactivity principles, they often rely on computational chemistry. Recent examples of this include: Cu(I) mediated alkynylation, BF3-promoted carbene-like C-H insertions, cascade reactions with 1,3-diynes to give polycyclic aromatic hydrocarbons (PAHs), multicomponent reactions with cyclic amines and protic nucleophiles, and reactions that permit the synthesis of structurally complex natural products. More recently, the researchers have developed aza-HDDA reactions and the underlying energetics are quite different from the all-carbon analogs. Calculations here have helped considerably in providing insights into this new mode of reactivity. DFT calculations are used to probe the HDDA energetics of these new HDDA substrates, and are crucial in substrate design for this project. The group is currently pursuing studies of an underexplored, related process that they call the pentadehydro-Diels-Alder (PDDA) reaction.

In conjunction with the Center for Sustainable Polymers, these researchers are also investigating new sustainable monomers that can engage in ring-opening polymerization (ROP) processes to give 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. The researchers use the concept of isodesmic reactions to compute the thermodynamic driving force (or not) for these ROP reactions. The data obtained can then be compared with experimentally determined enthalpic and entropic contributions to the free energy change.

Finally, the group has a growing interest in understanding the electronic properties of some of the structurally novel and highly conjugated polycylic aromatic hydrocarbons that they can efficiently prepare using their HDDA chemistry. The molecular orbitals, especially the frontier HOMOs and LUMOs, of these systems are probed because of their importance to the absorption and emission properties of these materials. Potential applications for these compounds include their incorporation into light-emitting diodes and photovoltaic devices.

Project Investigators

Elson Santiago de Alvarenga
Ethan Gormong
Alexander Guzman
Professor Thomas Hoye
Mengyuan Jin
Trinadh Kaicharla
Paul Kevorkian
Niklas Kraemer
Sangjun Lee
William Rears
Casey Ritts
Jingyang Shi
Dorian Sneddon
Rong Tang
Katharine Toll
Ruiqin Wang
Juekun Wen
Arianna Wheeler
Xiao Xiao
Qian Xu
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