New Chemistry Enabled by Aryne Intermediates

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The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Daesung Lee. Professor Lee is a faculty member in the Department of Chemistry at the University of Illinois at Chicago. He is developing new classes of synthetic transformations that take advantage of highly reactive chemical compounds known as arynes. Arynes they have enough internal energy in their chemical bonds to enable the synthesis of highly strained, four-membered cyclic structures that are often used to make pharmaceuticals, molecular scaffolds for bioactive natural products, and other functional materials. Professor Lee is using an established reaction to carefully assemble arynes that are tethered to trapping groups. The project includes synthetic method development, mechanistic studies, and natural product synthesis. Professor Lee's group is well positioned to provide a high level of education and training for a wide variety of students. A summer research internship for undergraduate and high school students is part of the project. This research benefits society by providing innovations to the chemical industry and medicine and by producing a highly technically-trained workforce.The relatively high electrophilic nature of arynes in combination with their tendency to interact with transition metal complexes provide a versatile platform for exploring new reactivity. This research focuses on novel transformations enabled by the high reactivity of silver-complexed aryne intermediates, which allows for the formation of a variety of four-membered ring structures as isolable products or as transient intermediates. Specific areas of research involve the exploration of four-membered ring-forming Alder-ene reaction by arynes relying on steric effect and hydrogen bonding elements and an investigation of chemo- and regioselectivity for Alder-ene and [2+2] cycloadditions employing various aryne-allene intermediates, and their application for the synthesis of herbindole B. Professor Lee also considers the development of a new synthetic method for the construction of chromanone derivatives relying on the aryne-carbonyl [2+2] cycloaddition reactions and of new annulation reactions of arynes with carbon-nitrogen multiple bonds to form novel heteroaromatic compounds. Exploration of benzocyclobutene derivatives for transition metal-catalyzed transformations is also under study. The educational plan includes a summer research program for high school students to introduce them to synthetic organic chemistry.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.