Copper-promoted site-selective carbonylation of sp3 and sp2 C-H bonds with nitromethane

Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation fea...

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Published inChemical science (Cambridge) Vol. 7; no. 8; pp. 5260 - 5264
Main Authors Wu, Xuesong, Miao, Jinmin, Li, Yanrong, Li, Guigen, Ge, Haibo
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 01.08.2016
Subjects
Amides
Carbonyls
Chemical bonds
Chemistry
Chemistry, Multidisciplinary
Cleavage
Compatibility
Functional groups
Isotope effect
Nitromethane
Physical Sciences
Science & Technology
UNACTIVATED C(SP)-H BONDS
NEF REACTION
ACTIVATION
1,3-AZOLES
COUPLING REACTIONS
ARYL HALIDES
BENZOIC-ACID DERIVATIVES
CATALYZED ALPHA-ARYLATION
CARBON-HYDROGEN BONDS
C(SP)-H
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Summary:Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp(3)C-H bond breaking step is reversible, whereas the sp(2)C-H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.
Bibliography:National Science Foundation
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ISSN:2041-6520
2041-6539
DOI:10.1039/c6sc01087c