Metal-based catalysts and reagents possess unique reactivity profiles that are inaccessible using conventional organic molecules and, consequently, occupy a privileged role in organic synthesis. We are investigating how organic radical ions–typically thought of as fleeting intermediates–can be tamed and exploited to expand the reactivity of bench-stable organic molecules. Our central hypothesis is that these organic radical ions will not only mimic the unique reactivity of metallic species but will also engender selectivity profiles inaccessible using existing synthetic tactics. Herein, we will describe two new reaction platforms based on persistent organic radical ions. In the first, we outline a blueprint to access a new family of photocatalysts with redox potentials far beyond the limits of conventional photoredox systems but with the same exquisite selectivity for radical processes. In the second, we will discuss a new approach to promote the oxidatively coupling of alkenes and common nucleophiles via a metastable dicationic intermediate.

Organic radical ions as catalysts and reagents: Extreme reactivity with unique selectivity

ACS Fall 2021

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