Mechanisms and Application of Dehydro-Diels-Alder Cycloadditions

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With this award, the Chemical Synthesis Program of the NSF Division of Chemistry is supporting the research of Professor Kay Brummond at the Department of Chemistry, University of Pittsburgh. Professor Brummond and her group are studying dearomative dehydro-Diels-Alder (DDDA) reactions using a combined experimental and computational approach in collaboration with the group of Professor Peng Liu. Elucidating details of the bond reorganization that occurs in these transformations is important so that chemists are better able to rationally expand the generality of the reaction. This chemistry is also of great value from an applications standpoint as predictable DDDA chemistry allows for control of the structural characteristics of the product that underlie the desirable physical properties of these systems. The findings from these investigations are being applied to the design of new strategies for preparing novel compounds of societal importance, in particular, high-performing organic photovoltaic materials. The collaborative approach is affording the next-generation of scientific problem-solvers and communicators equipped with a breadth of experience and chemical expertise to ask the right questions and provide innovative solutions. Professor Brummond is also combining training and mentoring of next generation of chemists with a top-down approach to implement diversity, equity, and inclusivity strategies at the departmental and college level, to provide a far-reaching and powerful platform for broadening participation of underrepresented groups in science, technology, engineering, and mathematics (STEM). The dehydro-Diels–Alder reaction is a powerful method for preparing highly unsaturated six-membered rings; however, when these reactions involve the dearomatization of a heteroarene, harsh conditions and the formation of multiple products compromise their usefulness. Professor Brummond and her research group are working to improve the synthetic utility of dearomative dehydro-Diels–Alder (DDDA) reactions by determining factors that control reactivity and product selectivity for heteroarenes. Both experimental and computational mechanistic studies are being performed in tandem to systematically establish electronic and steric trends, as well as increase computational reliability. Computational studies are being done in collaboration with the research group of Professor Peng Liu, also at the University of Pittsburgh. Expansion of the synthetic utility of the DDDA reaction is also being achieved through the synthesis of novel ladder-type heteroarene compounds. Convergent methods to design and synthesize high performing organic photovoltaic materials from these ladder-type conjugated structures are being developed and will provide valuable alternatives to cross-coupling approaches. The target selection process is being guided by computational property predictions performed by an expert in theoretical modeling and simulation of organo-electronic materials. Professor Brummond is committed to broadening participation in STEM by increasing diversity, equity, and inclusivity (DEI) in chemistry specifically and in the natural sciences using methodology that incorporates both a bottom-up approach, maintaining an active research group focused on advising and mentoring the next generation of organic chemists, and a top-down approach, leveraging her position as an academic leader and associate dean for the Kenneth P. Dietrich School of Arts and Sciences, to champion evidence-based strategies to change culture, policies, and practices to close DEI gaps in the sciences.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.