In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Dennis P. Curran of the Department of Chemistry at University of Pittsburgh will explore objectives in small molecule synthesis, polymer synthesis, and main group chemistry. Mechanistic experiments will be conducted to better understand newly discovered boryl radical homolytic substitution reactions with disulfides. The results will be used to develop new conditions for polarity reverse catalysis (PRC) reductions with NHC-boranes and to develop NHC-boranes as coinitiators for Type I and Type II radical photopolymerizations. Reactions of carbon-centered radicals with boron substituents will be studied and the products will be used for new kinds of cross coupling reactions. NHC-boranes will be developed as safe and practical reagents for common types of preparative hydride reductions. New methods for hydroboration based on borenium catalysts [NHC-BH2]+ will be developed. These could supplant transition-metal catalyzed reactions.
The concepts and methods of this work deepen and broaden the disciplines of small molecule and polymer synthesis and help in the quest to provide the molecules, materials, and technologies that other disciplines that rely on to progress. There is a broad focus on sustainable chemistry with the common second row element boron (readily available, not toxic, easily reused) replacing rare, expensive or toxic elements. There is a strong coupling of advancing the frontiers of science with teaching, training and learning of the diverse group of undergraduate students and graduate students who do the day-to-day research work. They move into the workplace to become the human capital that drives progress in many areas that are vital to the health of our citizenry and the economy of our nation. The project also regularly uses technology like videoconferences to manage intercontinental collaborations. These collaborations expand the direct teaching/training impact of the proposal beyond Pittsburgh to Lyon and Mulhouse in France.