Organocatalytic Enantioselective Sigmatropic Rearrangements to Probe Divergent Reactivity of Reactive Intermediates

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Divergent reactivity is a phenomenon that occurs when reacting molecules can follow two competing reaction pathways, each leading to different products. This reactivity can be both an advantage and disadvantage in the synthesis of organic molecules. If the factors dictating the reaction pathways are well understood, divergent reactivity can be deliberately manipulated and harnessed to advantage. When this fundamental understanding is lacking, however, this dual reactivity diminishes synthetic utility. In this project, with the support from the Chemical Catalysis Program of the Chemistry Division, Professor Brenner-Moyer of Rutgers University-Newark is investigating the influence of catalysts on divergent reactivity. Catalysts are substances that increase the rates of chemical reactions but are themselves not consumed, and are of enormous importance in fundamental and industrial chemistry. This knowledge gained from this research ultimately enables improved control of reaction outcomes, permitting direct access to useful chemicals. Professor Brenner-Moyer and her group are especially interested in new strategies to synthesize alkaloids, which are a broad class of naturally occurring compounds that exhibit a range of biological activities. Professor Brenner-Moyer is also coordinating a peer-mentoring program for academically at-risk, first-year female students interested in the sciences, with the goal of increasing their retention as STEM (science, technology, engineering, mathematics) majors. In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Brenner-Moyer of the Department of Chemistry at Rutgers University-Newark is investigating catalyst control in reactions of dienamine and ammonium ylide intermediates through the lens of new reaction development. These investigations entail a combination of synthetic studies, including the design and synthesis of new reaction catalysts, and synthetic mechanistic studies. Findings of these studies improve catalysts used in divergent reactions; this is a crucial step in harnessing their enormous synthetic potential for advanced manufacturing. Specifically, attaining generally accepted models for catalyst control of dienamine and ammonium ylide intermediates enables access to valuable enantiopure, remotely functionalized aldehyde synthons and complex alkaloid structures, respectively. Concurrent with these research activities, Professor Brenner-Moyer also coordinates a peer-mentoring program for first-year female Louis Stokes Alliances for Minority Participation (LSAMP) and Educational Opportunity Fund (EOF) students designed to increase their retention as STEM majors.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.