Catalytic Acceptorless Dehydrogenation of Aliphatic Alcohols

We developed the first acceptorless dehydrogenation of aliphatic secondary alcohols to ketones under visible light irradiation at room temperature by devising a ternary hybrid catalyst system comprising a photoredox catalyst, a thiophosphate organocatalyst, and a nickel catalyst. The reaction procee...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 142; no. 9; pp. 4493 - 4499
Main Authors Fuse, Hiromu, Mitsunuma, Harunobu, Kanai, Motomu
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 04.03.2020
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
OXIDATION
HYDROGEN
SUBSTITUTION
ACID
PHOTOREDOX
ESTERS
ALDEHYDES
BEARING
LIGAND
N-HETEROCYCLES
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Summary:We developed the first acceptorless dehydrogenation of aliphatic secondary alcohols to ketones under visible light irradiation at room temperature by devising a ternary hybrid catalyst system comprising a photoredox catalyst, a thiophosphate organocatalyst, and a nickel catalyst. The reaction proceeded through three main steps: hydrogen atom transfer from the α-C–H bond of an alcohol substrate to the thiyl radical of the photo-oxidized organocatalyst, interception of the generated carbon-centered radical with a nickel catalyst, and β-hydride elimination. The reaction proceeded in high yield under mild conditions without producing side products (except H2 gas) from various alcohols, including sterically hindered alcohols, a steroid, and a pharmaceutical derivative. This catalyst system also promoted acceptorless cross-dehydrogenative esterification from aldehydes and alcohols through hemiacetal intermediates.
Bibliography:ObjectType-Article-1
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c00123