Guest-dependent conformation of 18-crown-6 tetracarboxylic acid: relation to chiral separation of racemic amino acids.
(+)-18-crown-6 tetracarboxylic acid (18C6H(4)) has been used as a chiral selector for various amines and amino acids. To further clarify the structural scaffold of 18C6H(4) for chiral separation, single crystal X-ray analysis of its glycine(+) (1), H3O+ (2), H5O2+ (3), NH4+ (4), and 2CH3NH3+ (5) complexes was performed and the guest-dependent conformation of 18C6H(4) was investigated. The crown ether ring of 18C6H4 in 3, 4, and 5 took a symmetrical C2 or C2-like conformation, whereas that in 1 and 2 took an asymmetric C1 conformation, which is commonly observed in complexes with various optically active amino acids. The overall survey of the present and related complexes suggests that the molecular conformation of 18C6H4 is freely changeable within an allowable range, depending on the molecular shape and interaction mode with the cationic guest. On the basis of the present results, we propose the allowable conformational variation of 18C6H4 and a possible transition pathway from its primary conformation to the conformation suitable for chiral separation of racemic amines and amino acids.
Nagata
Hiroomi
H
Mitsubishi Tanabe Pharma Corporation, Yodogawa-ku, Osaka 532-8505, Japan. nagata.hiroomi@md.mt-pharma.co.jp
Nishi
Hiroyuki
H
Kamigauchi
Miyoko
M
Ishida
Toshimasa
T
D000596:Amino Acids / Q000737:chemistry* / Q000302:isolation & purification*; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D043844:Crown Ethers / Q000737:chemistry*; D018360:Crystallography, X-Ray; D019075:Electrophoresis, Capillary / Q000379:methods; D006860:Hydrogen Bonding; D007202:Indicators and Reagents; D008958:Models, Molecular; D008968:Molecular Conformation; D055672:Static Electricity; D013237:Stereoisomerism
D000596:Amino Acids; D043844:Crown Ethers; D007202:Indicators and Reagents