ABR: Using Alkynes to Fuel the Generation of Reactive Intermediates

With funding from the Chemical Synthesis Program of the Division of Chemistry, Dr. Hoye and his research group at University of Minnesota will i) capitalize on underdeveloped or ii) discover entirely new reactions in organic chemistry. Alkynes are a class of compounds containing a carbon-carbon triple bond. They have inherently high potential energy, which means they can undergo chemical reactions that are more energetically (thermodynamically) favorable than for the functional groups present in many other types of organic chemicals. This reactivity is perhaps most familiar in the form of an acetylene (ethyne, the simplest alkyne) torch, which gives off considerably more heat than, say, methane (natural gas) when combusted with oxygen to give carbon dioxide and water. This energetic driving force can be used to design reactions using more complex alkynes to fuel the formation of reactive organic intermediates that undergo further reactions to give structurally interesting new molecules. These scientific advances have the possibility of opening new avenues for synthesis of compounds of value to other researchers engaged in the discovery of new compounds that have beneficial societal impact (e.g., pharmaceuticals, agrochemicals, or electronic/photonic device components). The student researchers who will engage in these studies will gain valuable skills from which they will launch their own careers. Dr. Hoye and his research group at University of Minnesota will capitalize on the potential energy housed by the alkyne functional group in designed organic reactants to serve as the thermodynamic driver to allow access to transient reactive intermediates. In addition to several ongoing investigations of aspects of triyne to benzyne conversion (the hexadehydro-Diels-Alder or HDDA reaction), they will exploit a recently discovered, two-alkyne-to-carbene reaction. Furthermore, unknown transformations of alkynes to produce, for example, nitrenes, highly strained ring systems, and cyclic 1,2-dienes or 1,2,3-trienes will be explored. The discovery of new reactions will continue to be the most important 'products' to emerge from this program. New and fundamentally important mechanistic knowledge will be produced in parallel with the synthetic advances. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.