A 0.005 mol amount of [Cp^*RhCl₂]₂ complex catalyzes reductive amination of acetophenone using ammonium formate in methanol at 50-70 °C give 1-phenylethylamine in 95% yield. The amine/alcohol and primary/secondary amine ratios are greater than 50 and 200, respectively. A variety of substrates including not only aryl ketones but also primary, secondary alkyl methyl ketones and a-keto acids can be used. With a-keto acids, a-amino acids are the products. In most cases only filtration is necessary to arrive at nearly pure a-amino acids in high yields. The novel catalytic system facilitates the Leuckart-Wallach-type reaction at a lower temperature with high chemoselectivity and generality. The reaction is clean and operationally simple. Other than the desired primary amine products the reaction produces only carbon dioxide and water, realizing an environmentally friend organic synthesis of primary amines.