Ruthenium-Catalyzed Selective Mono N-Ethylation of Arylamines and Tandem Reduction/N-Ethylation of Nitroarenes Using Triethylamine and Formic Acid.

The mono N-alkylation of arylamines using alkylamines as alkyl group donors has been scarcely investigated. In this work, we report the mono N-alkylation of several arylamines (52-95%) catalyzed by the complex ruthenium-triphos in the presence of Al(OTf)3. Moreover, the highly reductant ability of the catalyst system allows the tandem reduction/N-alkylation of nitrobenzenes in good yields (up to 80%). In addition, the catalyst can be recycled after three reaction cycles without loss of catalyst activity.

Selective reduction of nitroarenes using Ru/C and CaH2.

Herein, we report an efficient and highly selective method for the reduction of aromatic, heteroaromatic and halonitro compounds using the readily available and cost-effective Ru/C as a catalyst along with unconventional CaH2 as a source of hydride. In most cases the corresponding anilines can be obtained by simple filtration without further purification. The use of 2-MeTHF and the simple operational work-up constitute a valid alternative to previous methodologies.