Designer Silver Catalysts for Selective Bond Amidations

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With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Jennifer Schomaker of the Department of Chemistry at the University of Wisconsin Madison to design new catalysts that convert feedstock chemicals into useful building blocks for the synthesis of pharmaceuticals and agrochemicals. The silver catalysts that are being developed change common parts of organic molecules called alkenes and alkanes into nitrogen-containing groups called amines. Importantly, these catalysts are also being tuned to select a specific type of alkene or alkane to undergo the amination process within a molecule containing multiple examples of alkane and/or alkene bonds. Professor Schomaker and her diverse team of graduate and undergraduate researchers are examining questions about how these catalysts work in order to learn how to improve their performance for the advanced manufacturing of chemicals and materials. Portions of this study are also being adapted for undergraduate teaching laboratory experiments to engage students at an early stage in research experiences. Green aspects of this project are being pursued in teaching laboratory course activities that provide guided inquiry opportunities for undergraduates.The development of low-cost, modular catalysts for the tunable conversion of C-H bonds to C-N bonds is a long-standing challenge that is crucial for achieving streamlined syntheses of important molecular fragments in pharmaceutical and material applications. To address this issue, Professor Schomaker and her research group are designing silver catalysts that can control the selective transformation of C-H bonds to C-N bonds through metal-catalyzed nitrene transfer processes. These investigations combine mechanistic, spectroscopic, and computational studies to understand how the different structural elements of the silver catalysts influence interactions with substrates and promote selective reactivity with specific C-H bonds. Case studies are also being explored to illustrate the impact of these new synthetic tools for the preparation of enantioenriched amines, the construction of synthetic building blocks for pharmaceuticals, and the design of novel amino sugars. Ultimately, this work is establishing general design principles for new silver catalysts that can override innate reactivity preferences and do not require a directing group for C-H amidation.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.