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. 2020 Jul 13;59(29):11845-11849.
doi: 10.1002/anie.202003959. Epub 2020 May 18.

Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton-Coupled Electron Transfer

Elaine Tsui  1 , Anthony J Metrano  1 , Yuto Tsuchiya  1 , Robert R Knowles  1
Affiliations

Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton-Coupled Electron Transfer

Elaine Tsui et al. Angew Chem Int Ed Engl. .

Abstract

We report a catalytic, light-driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible-light irradiation in the presence of an IrIII -based photoredox catalyst, a Brønsted base catalyst, and a hydrogen-atom transfer (HAT) co-catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O-H bonds through a proton-coupled electron-transfer mechanism. This method exhibits a broad substrate scope and high functional-group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented.

Keywords: alcohols; ethers; hydroetherification; photocatalysis; radicals.

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Figures

Scheme 1.
Scheme 1.
(a) Traditional approaches to hydroetherification typically involve alkene activation mechanisms. (b) Development of a general strategy for hydroalkoxylation via O–H bond activation. (c) PCET-mediated hydroetherification of unactivated alkenes.
Scheme 2.
Scheme 2.
Prospective catalytic cycle.
See this image and copyright information in PMC

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