CAREER: Mechanism-Guided Remote Multifunctionalization of Unsaturated Hydrocarbons

This project will develop methods to control the selectivity of multifunctionalization reactions, which would enable production of complex valuable chemicals from simple inexpensive starting materials. Multifunctionalization reactions involve multiple bond-breaking and making steps in a single reaction and can be used to rapidly increase the molecular complexity, and value, of abundant hydrocarbon feedstocks. However, poor selectivity in these transformations often leads to an unusable mixture of products. The research team under Dr. Bruch will investigate how specifically designed substrates can be used to address this challenge and develop clear rules for broad implementation. The project will train undergraduate and graduate students to investigate the molecular details of organometallic catalysis and the design of new catalytic reactions to facilitate the synthesis of products with pharmaceutical, materials, and energy applications. Furthermore, the project will support (i) the development of a summer workshop series to improve the technical, software, and data analysis skills of undergraduate and graduate students and (ii) a hybrid workshop-conference for undergraduates that provides training in science communication with general and technical audiences. This project will examine and evaluate how remote leaving groups can be used to control the regioselective multifunctionalization of unsaturated hydrocarbons. The key premise of this work is that the initial functionalization can be used to activate a remote leaving group, thereby creating a trigger for controlling the multifunctionalization reaction cascade. Initial targets will focus on the deaminative multifunctionalization of alkenes, alkynes, and allenes before targeting the activation of remote C–O and C–F bonds. These studies will be coupled with detailed mechanistic and kinetic investigations in order to identify different modes of control and enable the divergent synthesis of valuable products from cheap, unified feedstocks. Overall, the project will advance our fundamental understanding of control in multifunctionalization reactions and afford access to products with unique substitution patterns of interest to commodity, materials, and pharmaceutical industries. 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. NSF Award ID: 2541341 | Program: 01002627DB NSF RESEARCH & RELATED ACTIVIT | Principal Investigator: Quinton Bruch | Institution: SUNY at Stony Brook, STONY BROOK, NY | Award Amount: $800,000 View on NSF Award Search: https://www.nsf.gov/awardsearch/show-award/?AWD_ID=2541341 View on Research.gov: https://www.research.gov/awardapi-service/v1/awards/2541341.html