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. 2011 Jun 8;133(22):8478-81.
doi: 10.1021/ja202769t. Epub 2011 May 12.

Nickel-catalyzed Kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates

Amruta Joshi-Pangu  1 , Chao-Yuan Wang, Mark R Biscoe
Affiliations

Nickel-catalyzed Kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates

Amruta Joshi-Pangu et al. J Am Chem Soc. .

Abstract

We report a Ni-catalyzed process for the cross-coupling of tertiary alkyl nucleophiles and aryl bromides. This process is extremely general for a wide range of electrophiles and generally occurs with a ratio of retention to isomerization >30:1. The same procedure also accommodates the use of aryl triflates, vinyl chlorides, and vinyl bromides as the electrophilic component.

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Figures

Figure 1.
Figure 1.
Proposed catalytic cycle for the Ni-catalyzed cross-coupling of tertiary alkyl nucleophiles and aryl halides.
Figure 2.
Figure 2.
NHC ligand screen for the Ni-catalyzed cross-coupling of t-BuMgCl and 4-bromoanisole.
Figure 3.
Figure 3.
The influence of NiCl2 · (H2O)n hydration on the cross-coupling of t-BuMgCl and 4-bromoanisole as shown in Figure 2.
Figure 4.
Figure 4.
Ni-catalyzed cross-coupling reaction of t-BuMgCl and vinyl electrophiles (ratio of retention product to isomerization product in parentheses).
See this image and copyright information in PMC

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