The use of microwave (MW) irradiation for the condensation reaction between acetophenone and alpha-phenylethylamine to prepare (R,R)-bis[alpha-phenylethyl]amine results in significantly reduced reaction times relative to the use of conventional heating. In this protocol, a secondary amine, (R,R)-bis(alpha-phenylethyl)amine is treated with acryloyl chloride to afford conjugated amide N,N-bis[(R)-alpha-phenylethyl]prop-2-enamide, (R,R)-3. 1,4-Addition of alpha-phenylethylamine to unsaturated (R,R)-3 affords propanamide N,N-Bis[(R)-alpha-phenylethyl]-3-N-[(S)-alpha-phenylethyl]amino-propanamide, (R,R,S)-4, which can be alkylated with high diastereoselectivity to give derivative N,N-Bis[(R)-alpha-phenylethyl]-3-N'-[(S)-alpha-phenylethyl]amino-propanamide, (R,R,S,S)-5. Hydrogenolysis of (R,R,S,S)-5 catalyzed by palladium hydroxide and final hydrolysis (4 N HCl) resulting in the formation of (S)-alpha-benzyl-beta-alanine, (S)-7, is facilitated by MW irradiation. The use of MW irradiation in this step prevents racemization of the desired amino acid. The present protocol constitutes one of the simplest strategies for the asymmetric synthesis of biologically relevant alpha-substituted-beta-amino acids since it takes advantage of inexpensive, commercially available beta-Ala and either (R)- or (S)-alpha-phenylethylamine as chiral auxiliary. The required time for this protocol is approximately 90 h, which can be carried out in 5 d.