A method for the highly regioselective reductive coupling reaction of N-aryl-伪-imino esters with dienes is described. The method utilizes the RuHCl(CO)(PPh3)3/iPrOH catalytic system under an Ar atmosphere and provides 伪-branched allylic 伪-amino acid derivatives. Application of this transformation to the concise synthesis of a natural plant growth regulator is demonstrated.