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Diastereo‐ and Enantioselective anti ‐Selective Hydrogenation of α‐Amino‐β‐keto Ester Hydrochlorides and Related Compounds Using Transition‐Metal–Chiral‐Bisphosphine Catalysts
Author(s) -
Hamada Yasumasa
Publication year - 2014
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.201300032
Subject(s) - asymmetric hydrogenation , enantioselective synthesis , kinetic resolution , chemistry , catalysis , iridium , transition metal , rhodium , noyori asymmetric hydrogenation , ruthenium , organic chemistry , amino acid , combinatorial chemistry , biochemistry
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.