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. 2012 May 14;23(8):1103-1107.
doi: 10.1055/s-0031-1290765.

The Use of Tertiary Alkylmagnesium Nucleophiles in Ni-Catalyzed Cross-Coupling Reactions

Amruta Joshi-Pangu  1 , Mark R Biscoe
Affiliations

The Use of Tertiary Alkylmagnesium Nucleophiles in Ni-Catalyzed Cross-Coupling Reactions

Amruta Joshi-Pangu et al. Synlett. .

Abstract

Nickel-catalyzed cross-coupling reactions of unactivated tertiary alkyl nucleophiles and aryl bromides have been developed using N-heterocyclic carbene ligands. These processes are reviewed alongside earlier attempts to employ unactivated tertiary alkyl nucleophiles in cross-coupling reactions. Potential mechanisms for the transformations, and future challenges in this field are discussed.

Keywords: Grignard reaction; cross-coupling; homogeneous catalysis; nickel; transition metals.

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Figures

Figure 1
Figure 1
NHC ligands employed by the Glorius group (5) and by the Biscoe group (6) in Ni-catalyzed cross-coupling reactions of t-BuMgCl and arylbromides
Scheme 1
Scheme 1
Hintermann’s method for the Cu-catalyzed cross-coupling of tertiary alkylmagnesium reagents and polychlorinated aza-aryl electrophiles
Scheme 2
Scheme 2
(a) Lei’s use of t-BuZnCl in a Pd-catalyzed cross-coupling reaction with an aryl iodide. (b) Hu’s stoichiometric treatment of a Ni pincer complex with t-BuMgCl.
Scheme 3
Scheme 3
Possible catalytic cycles for Ni- and Pd-catalyzed cross-coupling reactions of alkyl nucleophiles and aryl halides
Scheme 4
Scheme 4
Side-products resulting from the competing β-hydride elimination pathway
Scheme 5
Scheme 5
Equilibrium between tricoordinate (NHC)2NiCl and its μ-chloronickel dimer
See this image and copyright information in PMC

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