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Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton‐Coupled Electron Transfer
Author(s) -
Tsui Elaine,
Metrano Anthony J.,
Tsuchiya Yuto,
Knowles Robert R.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202003959
Subject(s) - catalysis , alkene , chemistry , photochemistry , proton coupled electron transfer , homolysis , electron transfer , intramolecular force , radical , reactive intermediate , hydrogen atom , substrate (aquarium) , proton , stereochemistry , organic chemistry , alkyl , oceanography , physics , quantum mechanics , geology
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 Ir III ‐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.