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Hydrogen Atom Transfer Driven Enantioselective Minisci Reaction of Alcohols

Published version
Peer-reviewed

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Authors

Colgan, Avene C 
Gibson, David C 
Chuentragool, Padon 
Lahdenperä, Antti SK 

Abstract

jats:titleAbstract</jats:title>jats:pCatalytic enantioselective Minisci reactions have recently been developed but all instances so far utilize α‐amino radical coupling partners. We report a substantial evolution of the enantioselective Minisci reaction that enables α‐hydroxy radicals to be used, providing valuable enantioenriched secondary alcohol products. This is achieved through the direct oxidative coupling of two C−H bonds on simple alcohol and pyridine partners through a hydrogen atom transfer (HAT)‐driven approach: a challenging process to achieve due to the numerous side reactions that can occur. Our approach is highly regioselective as well as highly enantioselective. Dicumyl peroxide, upon irradiation with 390 nm light, serves as both HAT reagent and oxidant whilst selectivity is controlled by use of a chiral phosphoric acid catalyst. Computational and experimental evidence provide mechanistic insight as to the origin of selectivity, revealing a stereodetermining deprotonation step distinct from the analogous reaction of amide‐containing substrates.</jats:p>

Description

Keywords

34 Chemical Sciences, 3405 Organic Chemistry, 3406 Physical Chemistry, Alcoholism, Alcohol Use and Health, Substance Misuse

Journal Title

Angewandte Chemie

Conference Name

Journal ISSN

0044-8249
1521-3757

Volume Title

Publisher

Wiley
Sponsorship
Engineering and Physical Sciences Research Council (EP/P020259/1)
European Research Council (757381)
Engineering and Physical Sciences Research Council (EP/S03269X/1)