Highly enantioselective extraction of underivatized amino acids by the uryl-pendant hydroxyphenyl-binol ketone

Haofei Huang, Qian Chen, Misun Choi, Raju Nandhakumar, Zhishan Su, Sihyun Ham, Kwan Mook Kim

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

The hydroxyphenyl chiral ketone, (S)-3, reacts with D-amino acids bearing hydrophobic side chains exclusively over the L-amino acids in a two-phase liquid-liquid extraction, and thus acts as a highly stereoselective extractant. Calculations for the energy-minimized structures for the imine diastereomers and the comparison of the selectivities with other phenyl ketones, (S)-4 and (S)-5, demonstrate that the hydrogen bond between the carboxylate group and the phenolic hydroxyl group contributes to the remarkable enantioselectivities. The multiple hydrogen bonds present in the imine of (S)-3 reinforce the rigidity, and results in the difference between the stabilities of the imine diastereomers. The imine could be hydrolyzed in methanolic HCl solution, and the extraction of the evaporated residues revived the organic layer of (S)-3, which could enter into a new extractive cycle and leaves the D-amino acid with enantiomeric excess (ee) values of over 97 % in the aqueous layer. Extracting with ELLE: The hydroxyphenyl-binol ketone forms an imine exclusively with D-amino acids (AA) under the condition of enantioselective liquid-liquid extraction (ELLE; see scheme). Multiple hydrogen bonds greatly increase the steric hindrance of the imine of L-amino acids, whose formation was not detected in the 1HNMR spectroscopic studies.

Original languageEnglish
Pages (from-to)2895-2900
Number of pages6
JournalChemistry - A European Journal
Volume20
Issue number10
DOIs
StatePublished - 3 Mar 2014

Keywords

  • amino acids
  • chirality
  • density functional calculations
  • enantioselectivity
  • hydrogen bonds
  • NMR spectroscopy

Fingerprint

Dive into the research topics of 'Highly enantioselective extraction of underivatized amino acids by the uryl-pendant hydroxyphenyl-binol ketone'. Together they form a unique fingerprint.

Cite this