Chapter IV.2 New Chiral Rh(I) and Ru(II) Complexes: Highly Efficient Catalysts for Homogeneous Asymmetric Hydrogenation

Abstract

Abstract Practical methods for the synthesis of (R)- or (S)-2,2′-bis(diaryl- or dialkylphosphino)-1,1′-binaphthyls (BINAPs) have been developed. These new axially dissymmetric di-tert-phosphines serve as excellent ligands for Rh(I)—catalyzed asymmetric hydrogenation of α-acylaminoacrylic acids and asymmetric isomerization of allylamines to enamines. New mononuclear BINAP—Ru(II) dicarboxylate complexes and cationic BINAP—Ru(II)—arene complexes have also been prepared. These complexes and their derivatives are highly efficient catalysts for asymmetric hydrogenation of enamides, alkyl- and aryl-substituted acrylic acids, β,γ-unsaturated carboxylic acids, allylic and homoallylic alcohols, and a variety of functionalized ketones such as β-keto esters, α-amino ketones, etc.