Ruthenium-catalyzed reductive deamination and tandem alkylation of aniline derivatives

• Catalytic transformations of aniline derivatives.
• Catalytic reductive deamination of N-alkyl o-acylanilines.
• Alkylation of N-alkyl o-acylanilines with olefins.

We developed two new catalytic transformations of anilines via oxidative addition of C–N bonds to ruthenium centers. One is ruthenium-catalyzed reductive deaminatoindeamination of N-alkylated o-acylanilines. The other one is catalytic coupling of N-alkylated o-acylanilines with olefins giving ortho-alkylated aromatic ketones via C–N bond cleavage. This reaction involves a ruthenium hydride species as an intermediate, formed after β-hydride elimination from the ruthenium amide species.

Reductive deamination of o-acylaniline derivatives was achieved by simply heating with RuH2(CO)(PPh3)3 catalyst via carbon–nitrogen bond cleavage. Tandem reductive deamination/alkylation of o-acylanilines was also found to proceed using the ruthenium catalyst in the presence of olefins.Figure optionsDownload as PowerPoint slide