Divergence between Organometallic and Single-Electron-Transfer Mechanisms in Copper(II)-Mediated Aerobic C–H Oxidation

Copper(II)-mediated C–H oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from CuII-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Und...

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Published inJournal of the American Chemical Society Vol. 135; no. 26; pp. 9797 - 9804
Main Authors Suess, Alison M, Ertem, Mehmed Z, Cramer, Christopher J, Stahl, Shannon S
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 03.07.2013
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
chlorination
Copper - chemistry
Electron Transport
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
oxidation
Oxidation-Reduction
Physical Sciences
quinoline
Science & Technology
PALLADIUM
ACTIVATION
DIRECT ARYLATION
N-CONFUSED PORPHYRIN
COPPER-CATALYZED OXIDATION
COMPLEXES
METALATION-DEPROTONATION MECHANISM
BOND FORMATION
TERMINAL ALKYNES
AROMATIC-SUBSTITUTION
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Summary:Copper(II)-mediated C–H oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from CuII-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Under basic conditions, the benzamide group undergoes directed C–H methoxylation or chlorination. Under acidic conditions, the quinoline group undergoes nondirected chlorination. Experimental and computational mechanistic studies implicate an organometallic C–H activation/functionalization mechanism under the former conditions and a single-electron-transfer mechanism under the latter conditions. This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding CuII-mediated C–H oxidation reactions.
Bibliography:National Science Foundation
ObjectType-Article-1
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content type line 23
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja4026424