Heck coupling with 4-iodo-3,5-dimethylphenyl acetate, promoted by palladium acetate and Tri(o-tolyl)-phosphine, is one of the key steps in a convenient asymmetric synthesis of the unnatural amino acid 2,6-dimethyl-L-tyrosine: Synthesis, 741 (1992). Asymmetric catalytic hydrogenation in supercritical carbon dioxide in the presence of a chiral rhodium catalyst gives the N-acetylalanine methyl ester in 99.5% ee: J. Am. Chem. Soc., 117, 8277 (1995). Undergoes rhodium-catalyzed addition with potassium organotrifluoroborates to give substituted alanine derivatives: Eur. J. Org. Chem., 69 (2004). In the presence of a Rh-BINAP catalyst, chiral amino acid derivaitives are formed with good ee: Angew. Chem. Int. Ed., 43, 719 (2004).
