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. 2012 Jun 20;134(24):9942-5.
doi: 10.1021/ja304561c. Epub 2012 Jun 12.

Benzylation of nitroalkanes using copper-catalyzed thermal redox catalysis: toward the facile C-alkylation of nitroalkanes

Peter G Gildner  1 , Amber A S Gietter, Di Cui, Donald A Watson
Affiliations

Benzylation of nitroalkanes using copper-catalyzed thermal redox catalysis: toward the facile C-alkylation of nitroalkanes

Peter G Gildner et al. J Am Chem Soc. .

Abstract

The C-alkylation of nitroalkanes under mild conditions has been a significant challenge in organic synthesis for more than a century. Herein we report a simple Cu(I) catalyst, generated in situ, that is highly effective for C-benzylation of nitroalkanes using abundant benzyl bromides and related heteroaromatic compounds. This process, which we believe proceeds via a thermal redox mechanism, allows access to a variety of complex nitroalkanes under mild reaction conditions and represents the first step toward the development of a general catalytic system for the alkylation of nitroalkanes.

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Figures

Figure 1
Figure 1
Examples of Ligands Examined in the Benzylation.
Scheme 1
Scheme 1
Alkylation of Nitronate Anions.
Scheme 2
Scheme 2
Electron-rich Copper Catalysts to Promote Nitroalkane Alkylation.
Scheme 3
Scheme 3
Sequential Double Benzylation of Nitroalkanes.
Scheme 4
Scheme 4
Possible Mechanistic Pathway.
See this image and copyright information in PMC

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