Predominant (S)-enantioselective inclusion of aryl methyl sulfoxides by (S)-isoleucyl-(S)-phenylglycines

J Org Chem. 2010 Feb 5;75(3):660-5. doi: 10.1021/jo902197k.

Abstract

In terms of chiral recognition for racemic aryl methyl sulfoxides in the solid state, three kinds of crystalline (S)-alkylglycyl-(S)-phenylglycines were examined as potential dipeptides host molecules. When (S)-alanyl-(S)-phenylglycines [(S,S)-Ala-Phg] crystallized with aryl methyl sulfoxides, the stereochemistry of preferentially included sulfoxides depended on the individual shapes of the sulfoxides and the enantiomeric excess was relatively low. Although (S)-leucyl-(S)-phenylglycines [(S,S)-Leu-Phg] and (S)-isoleucyl-(S)-phenylglycines [(S,S)-Ile-Phg] mainly included the S-form of aryl methyl sulfoxides, the enantiomeric recognition of (S,S)-Ile-Phg was superior to that of (S,S)-Leu-Phg. Single-crystal X-ray analysis of these inclusion compounds revealed that the dipeptide molecules self-assembled to form layer structures and included sulfoxides between these layers through hydrogen bonding between the proton of (+)NH(3) and the oxygen of the sulfoxide. Besides these host-guest interactions, the phenyl groups of the sulfoxides interacted with each other through the phenyl-phenyl interaction. Two adjacent homochiral sulfoxides make a pair having a 2-fold screw axis along the channel cavity. Thus, the self-recognition of sulfoxides made 2(1) helical column structures and had high enantioselectivity.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Glycine / analogs & derivatives*
  • Glycine / chemistry
  • Hydrogen Bonding
  • Isoleucine / chemistry*
  • Molecular Structure
  • Stereoisomerism
  • Structure-Activity Relationship
  • Sulfoxides / chemistry*

Substances

  • Sulfoxides
  • Isoleucine
  • 2-phenylglycine
  • Glycine