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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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202003959
Subject(s) - catalysis , photochemistry , alkene , chemistry , homolysis , proton coupled electron transfer , radical , intramolecular force , electron transfer , reactive intermediate , hydrogen atom , proton , substrate (aquarium) , stereochemistry , organic chemistry , alkyl , physics , quantum mechanics , oceanography , 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.