Olefin hydroetherification reactions constitute a versatile and atom-economical approach to C–O bond formation and the construction of oxygen-containing heterocycles, which are common structural motifs in natural products and medicinal agents. We report a general protocol for the catalytic, light-driven hydroetherification of unactivated alkenols to furnish cyclic ether products. Facilitated by direct homolytic activation of alcohol O–H bonds<i> via </i>proton-coupled electron transfer, 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 catalyst, and a hydrogen atom transfer co-catalyst. This method exhibits a broad substrate scope and high functional group tolerance, and it accommodates a wide range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification and intermolecular hydroetherification reactions are also presented.

Catalytic etherification of unactivated olefins enabled by proton-coupled electron transfer

ACS Spring 2022

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