Olefin hydroetherification reactions have long been sought after, as they represent a versatile and atom-economical approach to C–O bond formation. Here, we report a general protocol for the light-driven, intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. Facilitated by proton-coupled electron transfer (PCET) activation of alcohol O–H bonds, these reactions proceed through an alkoxy radical intermediate, followed by addition to a pendent olefin. These transformations occur under visible light irradiation in the presence of an iridium(III) photocatalyst, a Brønsted base, and a hydrogen atom transfer catalyst. This method exhibits a broad substrate scope, high functional group tolerance, and applicability to a diverse range of alkene substitution patterns. Taken together, this strategy represents an advance in radical-based hydroalkoxylation methods. Results demonstrating the extension of this catalytic system to carboetherification are also presented.

Hydroetherification of unactivated alkenes enabled by light-driven proton-coupled electron transfer

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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