Products Cited in Publications Worldwide Electrochemical DABCOylation enables challenging aromatic C–H amination

Electrochemical DABCOylation enables challenging aromatic C–H amination

Stewart, Griffin; Alvarez, Eva Maria; Rapala, Chris; Sklar, Jonathan; Kalow, Julia A; Malapit, Christian A

DOI:

Abstract

The selective amination of aromatic C–H bonds is a powerful strategy to access aryl amines, functionalities found in many pharmaceuticals and agrochemicals. Despite advances in the field, platform for the direct, selective C–H amination of electronically diverse (hetero)arenes, particularly electron-deficient (hetero)arenes, remains an unaddressed fundamental challenge.1-10 In addition, ma (hetero)arenes present difficulty in common selective pre-functionalization reactions, such halogenation11, or metal-catalyzed borylation12 and silylation13. Here, we report a general solution to these limitations that enables selective C–H amination across a comprehensive scope of (hetero)arenes. Key to this strategy’s success is the oxidative generation of highly electrophilic N-radical dications from bicyclic tertiary amines (DABCO) that reacts across a wide range of arenes with high selectivity. Notably, this platform constitutes the first anodically generated N-radical cations that enga in aromatic C–H amination over well-reported hydrogen atom transfer (HAT) with weak C–H bonds.14-16 This C–H amination reaction that allows selective functionalization of both electron-rich and deficie arenes, as well as pyridines, is a rarity in the general area of non-directed aromatic C–H functionalization.1-4 This sustainable electrochemical DABCOylation reaction provides access to many complex drug-like aryl- and pyridinylpiperazines with high functionality tolerance, chemoselectivity, and site-selectivity.17

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Tris(2-phenylpyridinato)iridium(III)

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Tris(2-phenylpyridinato)iridium(III)

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