δ‑Selective Functionalization of Alkanols Enabled by Visible-Light-Induced Ligand-to-Metal Charge Transfer

We demonstrate the application of ligand-to-metal charge transfer (LMCT) excitation to the direct catalytic generation of energetically challenging alkoxy radicals from alcohols through a coordination–LMCT–homolysis process with an abundant and inexpensive cerium salt as the catalyst. This catalytic...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 140; no. 5; pp. 1612 - 1616
Main Authors Hu, Anhua, Guo, Jing-Jing, Pan, Hui, Tang, Haoming, Gao, Zhaobo, Zuo, Zhiwei
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 07.02.2018
Amer Chemical Soc
Subjects
alcohols
carbon-hydrogen bond activation
catalysts
cerium
chemical bonding
Chemistry
Chemistry, Multidisciplinary
free radicals
Physical Sciences
Science & Technology
OXIDATION
INTRAMOLECULAR HYDROGEN ABSTRACTION
C(SP)-H BONDS
AMINATION
ALKYLATION
COMPLEXES
SATURATED ALCOHOLS
RADICALS
EFFICIENT
PHOTOREDOX CATALYSIS
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ISSN0002-7863
1520-5126
1520-5126
DOI10.1021/jacs.7b13131

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Summary:We demonstrate the application of ligand-to-metal charge transfer (LMCT) excitation to the direct catalytic generation of energetically challenging alkoxy radicals from alcohols through a coordination–LMCT–homolysis process with an abundant and inexpensive cerium salt as the catalyst. This catalytic manifold provides a simple and efficient way to utilize the characteristic reactivity and selectivity of transient alkoxy radicals for δ-selective C–H bond functionalization. Under mild redox-neutral conditions without the need for prefunctionalization, this method provides a versatile platform to access molecular complexity from simple and abundant alcohols.
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ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/jacs.7b13131