Derivatives of para-and meta-phenylene bis-alanine and related biphenyl systems, carrying four orthogonal protecting groups, were synthesised via combinations of Heck couplings and asymmetric hydrogenations. The intermediate unsaturated arylalanine derivatives were hydrogenated using [Rh (COD)((R, R)-DIPAMP)]+ BF4− or [Rh (COD)(Me-DuPHOS)]+ X− as catalysts to produce the optically active, protected amino acid derivatives in≥ 98% ee as ...