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 towards developing a general catalytic system for the alkylation of nitroalkanes.

Controlling the molecular topology of electrode–catalyst interfaces is a critical factor in engineering devices with specific electron transport kinetics and catalytic efficiencies. As such, the development of rational methods for the modular construction of tailorable electrode surfaces with robust molecular wires (MWs) exhibiting well-defined molecular topologies, conductivities and morphologies is critical to the evolution and implementation of electrochemical arrays for sensing and catalysis. In response to this need, we have established modular on-surface Sonogashira and Glaser cross-coupling processes to synthetically install arrays of ferrocene-capped MWs onto electrochemically functionalized surfaces. These methods are of comparable convenience and efficiency to more commonly employed Huisgen methods. Furthermore, unlike the Huisgen reaction, this new surface functionalization chemistry generates modified electrodes that do not contain unwanted ancillary metal binding sites, while allowing the bridge between the ferrocenyl moiety and electrode surface to be synthetically tailored. Electrochemical and surface analytical characterization of these platforms demonstrate that the linker topology and connectivity influences the ferrocene redox potential and the kinetics of charge transport at the interface.

Using a simple copper catalyst, the alkylation of nitroalkanes with α-bromocarbonyls is now possible. This method provides a general, functional group tolerant route to β-nitrocarbonyl compounds, including nitro amides, esters, ketones, and aldehydes. The highly sterically dense, functional group rich products from these reactions can be readily elaborated into a range of complex nitrogen-containing molecules, including highly substituted β-amino acids.

General Route for Preparing -Nitrocarbonyl Compounds Using Copper Thermal Redox Catalysis. --Nitrocarbonyl compounds are synthesized by using copper thermal redox catalysis from readily available -bromocarbonyls. This method provides a general, functional group tolerant route to -nitrocarbonyl compounds, including nitro amides, esters, ketones, and aldehydes. The versatile products from the reaction offer a range of options for additional synthetic manipulations, including access to highly substituted -amino acids and their derivatives. -(GIETTER, A. A. S.; GILDNER, P. G.; CINDERELLA, A. P.; WATSON*, D. A.; Org. Lett. 16 (2014) 11, 3166-3169, http://dx.

The in situ generated Cu(I) catalyst is highly effective for C‐benzylation of nitroalkanes via reduction of the benzyl bromides to the corresponding radicals.