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  4. Functional group tolerant Kumada-Corriu-Tamao coupling of non-activated alkyl halides with aryl and heteroaryl nucleophiles: Catalysis by a nickel pincer complex permits the coupling of functionalized Grignard reagents
 
research article

Functional group tolerant Kumada-Corriu-Tamao coupling of non-activated alkyl halides with aryl and heteroaryl nucleophiles: Catalysis by a nickel pincer complex permits the coupling of functionalized Grignard reagents

Vechorkin, Oleg  
•
Proust, Valérie
•
Hu, Xile  
2009
Journal of the American Chemical Society

A nickel(II) pincer complex [(MeNN2)NiCl] (1) catalyzes Kumada−Corriu−Tamao cross coupling of nonactivated alkyl halides with aryl and heteroaryl Grignard reagents. The coupling of octyl bromide with phenylmagnesium chloride was used as a test reaction. Using 3 mol % of 1 as the precatalyst and THF as the solvent, and in the presence of a catalytic amount of TMEDA, the coupling product was obtained in a high yield. The reaction conditions could be applied to cross coupling of other primary and secondary alkyl bromides and iodides. The coupling is tolerant to a wide range of functional groups. Therefore, alkyl halides containing ester, amide, ether, thioether, alcohol, pyrrole, indole, furan, nitrile, conjugated enone, and aryl halide moieties were coupled to give high isolated yields of products in which these units stay intact. For the coupling of ester-containing substrates, O-TMEDA is a better additive than TMEDA. The reaction protocol proves to be efficient for the coupling of Knochel-type functionalized Grignard reagents. Thus aryl Grignard reagents containing electron-deficient and/or sensitive ester, nitrile, amide, and CF3 substituents could be successfully coupled to nonactivated and functionalized alkyl iodides. The catalysis is also efficient for the coupling of alkyl iodides with functionalized heteroaryl Grignard reagents, giving rise to pyridine-, thiophene-, pyrazole-, furan-containing molecules with additional functionalities. Concerning the mechanism of the catalysis, [(MeNN2)Ni-(hetero)Ar] was identified as an intermediate, and the activation of alkyl halides was found to take place through a radical-rebound process.

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Type
research article
DOI
10.1021/ja9027378
Web of Science ID

WOS:000268399800037

Author(s)
Vechorkin, Oleg  
Proust, Valérie
Hu, Xile  
Date Issued

2009

Published in
Journal of the American Chemical Society
Volume

131

Issue

28

Start page

9756

End page

9766

Subjects

Carbon Bond Formation

•

Possessing Beta-Hydrogens

•

Suzuki Cross-Couplings

•

Arylmagnesium Reagents

•

19-Electron Complexes

•

Reductive Elimination

•

Oxidative Addition

•

Forming Reactions

•

Palladium

•

Bromides

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSCI  
Available on Infoscience
June 9, 2009
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/40363
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