Predominant (S)-enantioselective inclusion of aryl methyl sulfoxides by (S)-isoleucyl-(S)-phenylglycines.
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.
Akazome
Motohiro
M
Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33 Yayoicho, Inageku, Chiba 263-8522, Japan. akazome@faculty.chiba-u.jp
Doba
Ai
A
Matsumoto
Shoji
S
Ogura
Katsuyuki
K
D005998:Glycine / Q000031:analogs & derivatives* / Q000737:chemistry; D006860:Hydrogen Bonding; D007532:Isoleucine / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013454:Sulfoxides / Q000737:chemistry*
D013454:Sulfoxides; D007532:Isoleucine; C008852:2-phenylglycine; D005998:Glycine