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  4. Nickel-Catalyzed Direct Alkylation of Terminal Alkynes at Room Temperature: A Hemilabile Pincer Ligand Enhances Catalytic Activity
 
research article

Nickel-Catalyzed Direct Alkylation of Terminal Alkynes at Room Temperature: A Hemilabile Pincer Ligand Enhances Catalytic Activity

Garcia, Pablo M. Perez  
•
Ren, Peng  
•
Scopelliti, Rosario  
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2015
Acs Catalysis

Direct coupling of alkyl halides with terminal alkynes provides an efficient and streamlined access to alkyl-substituted alkynes, which are important synthetic intermediates, biologically active molecules, and organic materials. However, until now,there have been fewer than a handful of catalytic methods available for this reaction, and detailed mechanistic studies have not been reported. Herein, we describe the design and development a new nickel pincer complex that catalyzes the direct coupling of primary alkyl halides with terminal alkynes at room temperature. The catalysis has a good substrate scope and high functional group tolerance. Kinetic data suggest that the new pincer ligand is hemilabile, and the dissociation of a labile amine donor is the (t)urnover-determining step of the catalysis. An intermediate Ni-alkynyl species has been isolated and structurally characterized. The reactivity of this species gives insight into the nature of the active species for the activation of alkyl halide.

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Type
research article
DOI
10.1021/cs501502u
Web of Science ID

WOS:000349275300075

Author(s)
Garcia, Pablo M. Perez  
Ren, Peng  
Scopelliti, Rosario  
Hu, Xile  
Date Issued

2015

Publisher

American Chemical Society

Published in
Acs Catalysis
Volume

5

Issue

2

Start page

1164

End page

1171

Subjects

nickel

•

Sonogashira coupling alkynylation

•

pincer complex

•

kinetics

•

alkylation

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSCI  
Available on Infoscience
May 29, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/114655
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