New functional chiral P-based ligands and application in ruthenium-catalyzed enantioselective transfer hydrogenation of ketones


MERİÇ N., KAYAN C., GÜRBÜZ N. , KARAKAPLAN M., Binbay N. E. , AYDEMİR M.

TETRAHEDRON-ASYMMETRY, vol.28, no.12, pp.1739-1749, 2017 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 28 Issue: 12
  • Publication Date: 2017
  • Doi Number: 10.1016/j.tetasy.2017.10.004
  • Title of Journal : TETRAHEDRON-ASYMMETRY
  • Page Numbers: pp.1739-1749

Abstract

Metal-catalyzed asymmetric transfer hydrogenation is a powerful and practical method for the reduction of ketones to produce the corresponding secondary alcohols, which are valuable building blocks in the pharmaceutical, perfume, and agrochemical industries. Hence, a series of novel chiral beta-amino alcohols were synthesized by chiral amines with regioselective ring opening of (S)-propylene oxide or reaction with (S)-(+)-2-hydroxypropyl p-toluenesulfonate by a straightforward method. The chiral ruthenium catalytic systems generated from [Ru(arene)(mu-Cl)Cl](2) complexes and chiral phosphinite ligands based on amino alcohol derivatives were employed in asymmetric transfer hydrogenation of ketones to give the corresponding optically active alcohols; (2S)-1-([(2.9-2-[(diphenylphosphanypoxylpropyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenylphosphinitobis[dichol-oro(eta(6)-benzene)ruthenium(II)] acts an excellent catalyst in the reduction of cl-naphthyl methyl ketone, giving the corresponding alcohol with up to 99% ee. The substituents on the backbone of the ligands were found to have a remarkable effect on both the conversion and enantioselectivity of the catalysts. Furthermore, this transfer hydrogenation is characterized by low reversibility under these conditions. (C) 2017 Elsevier Ltd. All rights reserved.