ENANTIORECOGNITION OF A NEW CHIRAL SELECTOR, BETA-CYCLODEXTRIN PERPHENYLCARBAMATE, AS STUDIED BY NMR-SPECTROSCOPY AND MOLECULAR-ENERGY CALCULATION

被引:23
作者
KURODA, Y
SUZUKI, Y
HE, JY
KAWABATA, T
SHIBUKAWA, A
WADA, H
FUJIMA, H
GOOH, Y
IMAI, E
NAKAGAWA, T
机构
[1] SHINWA CHEM IND LTD,FUSHIMI KU,KYOTO 612,JAPAN
[2] TAISHO PHARMACEUT IND CO LTD,HIGASHI KU,NAGOYA,AICHI 461,JAPAN
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1995年 / 09期
关键词
D O I
10.1039/p29950001749
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The mechanism of enantioselective binding of chiral atenolol (AT)by beta-cyclodextrin perphenylcarbamate (PhCD) has been studied by NMR spectroscopy and by molecular modelling techniques including conformational and free energy of binding calculations for the AT-PhCD complexes. Among the various models tested, the (R)-enantiomer was found from the calculations to bind with the PhCD with its asymmetric carbon moiety inside the toroid of cyclodextrin, while its aromatic ring is outside the toroidal cavity al the secondary hydroxy group side; in contrast, the (S) counterpart preferred to-locate its aromatic ring inside the toroid, while retaining the asymmetric carbon moiety outside the cavity at the primary hydroxy group side. The differential changes in H-1 NMR chemical shifts and linewidths between the enantiomers of AT, caused as a result of interaction with PhCD, clearly reflected the difference in the binding mode suggested from the present molecular modelling calculations. It was concluded that although the binding affinity of (S)-AT is weaker than that of(R)-AT, the mobility of the (S)-enantiomer is lowered more than the (R) counterpart as a result of the interaction with PhCD.
引用
收藏
页码:1749 / 1759
页数:11
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