title: Diastereo- and enantioselective anti-selective hydrogenation of α-amino-β-keto ester hydrochlorides and related compounds using transition-metal-chiral-bisphosphine catalysts.
abstract: This review describes our recent works on the diastereo- and enantioselective synthesis of anti-β-hydroxy-α-amino acid esters using transition-metal-chiral-bisphosphine catalysts. A variety of transition metals, namely ruthenium (Ru), rhodium (Rh), iridium (Ir), and nickel (Ni), in combination with chiral bisphosphines, worked well as catalysts for the direct anti-selective asymmetric hydrogenation of α-amino-β-keto ester hydrochlorides, yielding anti-β-hydroxy-α-amino acid esters via dynamic kinetic resolution (DKR) in excellent yields and diastereo- and enantioselectivities. The Ru-catalyzed asymmetric hydrogenation of α-amino-β-ketoesters via DKR is the first example of generating anti-β-hydroxy-α-amino acids. Complexes of iridium and axially chiral bisphosphines catalyze an efficient asymmetric hydrogenation of α-amino-β-keto ester hydrochlorides via dynamic kinetic resolution. A homogeneous Ni-chiral-bisphosphine complex also catalyzes an efficient asymmetric hydrogenation of α-amino-β-keto ester hydrochlorides in an anti-selective manner. As a related process, the asymmetric hydrogenation of the configurationally stable substituted α-aminoketones using a Ni catalyst via DKR is also described.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba, 260-8675, Japan. y-hamada@faculty.chiba-u.jp.
authors.forename: Yasumasa
authors.initials: Y
authors.lastname: Hamada
mesh_terms: D000596:Amino Acids / Q000737:chemistry; D002384:Catalysis; D004952:Esters; D006865:Hydrogenation; D007700:Kinetics; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D000596:Amino Acids; D004952:Esters; D010720:Phosphines; D028561:Transition Elements; C044646:phosphine
keywords: diastereoselectivity; dynamic kinetic resolution; enantioselectivity; hydrogenation; transition metals