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. 2010 Feb 3;132(4):1264-6.
doi: 10.1021/ja909689t.

Nickel/bis(oxazoline)-catalyzed asymmetric Kumada reactions of alkyl electrophiles: cross-couplings of racemic alpha-bromoketones

Sha Lou  1 , Gregory C Fu
Affiliations

Nickel/bis(oxazoline)-catalyzed asymmetric Kumada reactions of alkyl electrophiles: cross-couplings of racemic alpha-bromoketones

Sha Lou et al. J Am Chem Soc. .

Abstract

The first asymmetric Kumada reactions of alkyl electrophiles are described, specifically, cross-couplings of racemic alpha-bromoketones with aryl Grignard reagents. Several features of this investigation are of interest. First, the couplings proceed at remarkably low temperature (-40 or -60 degrees C), which enables the asymmetric synthesis of racemization-prone alpha-arylketones. Second, dialkyl ketones undergo enantioselective coupling in good ee and yield. Third, readily available bis(oxazolines) are shown for the first time to be effective ligands for cross-couplings of alkyl electrophiles, thereby opening the door to new opportunities in asymmetric catalysis.

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References

    1. For a historical overview, see:Seyferth D. Organometallics. 2009;28:1598–1605.

    1. For pioneering studies of nickel-catalyzed processes, see:Tamao K, Sumitani K, Kumada M. J. Am. Chem. Soc. 1972;94:4374–4376.Corriu RJP, Masse JP. Chem. Commun. 1972:144.

    1. For overviews of cross-coupling chemistry, see:de Meijere A, Diederich F, editors. Metal-Catalyzed Cross-Coupling Reactions. Wiley–VCH; New York: 2004. Miyaura N, editor. Topics in Current Chemistry. Vol. 219. Springer–Verlag; New York: 2002.

    1. For example, see:Tamura M, Kochi J. Synthesis. 1971:303–305.

    1. For some recent work on nickel-catalyzed Kumada reactions of alkyl electrophiles (including leading references), see:Terao J, Kambe N. Acc. Chem. Res. 2008;41:1545–1554.Vechorkin O, Proust V, Hu X. J. Am. Chem. Soc. 2009;131:9756–9766.

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