Exploiting Mechanistic Knowledge to Develop Selective and Robust Synthetic n,pi-star Photochemistry

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Professor Zarko Boskovic of the University of Kansas is developing new photochemical reactions to create valuable molecules efficiently and selectively. Robust reaction conditions will enable access to diverse and structurally intricate compounds. Such compounds are important in drug-discovery research. Understanding how molecules behave after absorbing light may lead to the next-generation chemical technologies that avoid the harsh conditions and waste associated with traditional synthetic methods. The project will also train students in interdisciplinary science that combines synthetic chemistry, physical organic chemistry, and computational modeling. Educational tools such as interactive chemistry software and coding modules will be developed to improve chemistry education and promote data literacy among students. The project will also preserve and share a collection of thousands of previously synthesized compounds for future research and discovery. This research will explore n,π* excited states, which are special high-energy states populated by molecules after absorbing light. These states will be used to develop new chemical reactions. The project will focus on three main goals: (1) generating reactive ylides from strained rings through light-induced sensitized decarbonylation, (2) controlling the stereochemistry of nitrogen-containing molecules to make four-membered azetidine rings, and (3) studying short-lived radical intermediates using advanced spectroscopic techniques in conjunction with light sources. The team will use visible light activation, custom-designed light-absorbing groups, and chiral anions and auxiliaries to control chemical reactivity. Computational models will help explain and predict reaction behavior. These studies aim to expand synthetic photochemistry while providing a deeper understanding of the mechanisms of photochemical transformations thus enabling more facile access to the new types of molecules. 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.