Chemoselective Activation of sp(3) vs sp(2) C-H Bonds with Pd(II)

The first selective coupling of a carbon nucleophile with methyl, ethyl, propyl, and butyl arenes in the absence of a directing group is described. Pd(OAc)(2) double C-H activation displays remarkable selectivity for the terminal methyl sites in alkyl arenes, rather than the more commonly observed a...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 137; no. 1; pp. 18 - 21
Main Authors Curto, John M., Kozlowski, Marisa C.
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 14.01.2015
Subjects
Acetates - chemistry
Catalysis
Chemistry
Chemistry, Multidisciplinary
Lactones - chemistry
Molecular Structure
Organometallic Compounds - chemistry
Physical Sciences
Science & Technology
FUNCTIONALIZATION
OXIDATION
TOLUENE DERIVATIVES
ACYLATION
ACIDS
COMPLEXES
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Summary:The first selective coupling of a carbon nucleophile with methyl, ethyl, propyl, and butyl arenes in the absence of a directing group is described. Pd(OAc)(2) double C-H activation displays remarkable selectivity for the terminal methyl sites in alkyl arenes, rather than the more commonly observed arene sp(2) C-H activation. Mechanistic studies indicate the intermediacy of an azlactone dimer, obtained from oxidation with Pd(OAc)(2), and are consistent with a Pd-catalyzed C-H activation vs a radical process. The observed reactivity establishes that typical reaction solvents (e.g., toluene) can readily participate in C-H activation chemistry.
Bibliography:NIH RePORTER
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/ja5093166