Nickel-catalyzed decarbonylation of -acylated N-heteroarenes.

Nickel-catalyzed decarbonylation of -acylated N-heteroarenes is developed. This method can be used to produce a variety of -aryl heteroarenes, including pyrroles, indoles, carbazoles and phenoxazines, using benzoic acid derivatives as arylating reagents. Arylnickelamide intermediates that are relevant to the catalytic reaction were characterized by X-ray crystallography.

Nickel-Mediated Decarbonylation of Simple Unstrained Ketones through the Cleavage of Carbon-Carbon Bonds.

Despite advances in methods for the decarbonylation of aldehydes, the decarbonylation of ketones has been met with limited success because this process requires the activation of two inert carbon-carbon bonds. All of the decarbonylation reactions of simple unstrained ketones reported to date require the addition of a stoichiometric rhodium complex. We report herein the nickel/N-heterocyclic carbene-mediated decarbonylation of simple diaryl ketones.

Nickel-Catalyzed Alkylative Cross-Coupling of Anisoles with Grignard Reagents via C-O Bond Activation.

We report nickel-catalyzed cross-coupling of methoxyarenes with alkylmagnesium halides, in which a methoxy group is eliminated. A wide range of alkyl groups, including those bearing β-hydrogens, can be introduced directly at the ipso position of anisole derivatives. We demonstrate that the robustness of a methoxy group allows this alkylation protocol to be used to synthesize elaborate molecules by combining it with traditional cross-coupling reactions or oxidative transformation.

Nickel-catalyzed reductive cleavage of aryl alkyl ethers to arenes in absence of external reductant.

The reductive cleavage of the C-O bonds of aryl ethers has great potential in organic synthesis. Although several catalysts that can promote the reductive cleavage of aryl ethers have been reported, all such systems require the use of an external reductant, , hydrosilane or hydrogen. Here, we report the development of a new nickel-based catalytic system that can cleave the C-O bonds of ethers in the absence of an external reductant.