Preparation of chiral and meso-crown ethers incorporating cyclohexane-1,2-diol derivatives as a steric barrier and their complexation with chiral and achiral amines

被引:58
作者
Naemura, K [1 ]
Tobe, Y [1 ]
Kaneda, T [1 ]
机构
[1] OSAKA UNIV,INST SCI & IND RES,IBARAKI,OSAKA 567,JAPAN
关键词
chiral crown ether; chiral azophenolic crown ether; meso-Crown ether; enantioselectivity in complexation; diastereotopic face selectivity in complexation;
D O I
10.1016/0010-8545(95)01189-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The design and synthesis of chiral crown ethers possessing a chiral recognition ability which carry great potential for separation of enantiomers and analytical purpose has become an important and rapidly growing field of host-guest chemistry. One of the advantages of crown ethers constructed using a synthetic chiral building block is that it is rather easy to modify the chiral cavity resulting in the improvement in enantiomer selectivity. Cyclohexane-1,2-diol derivatives such as cis-1-phenylcyclohexane-1,2-diol, trans-1-phenylcyclohexane-1,2-diol and trans-1,2-diphenylcyclohexane-1,2-diol are of interest as chiral building blocks of crown ethers, because incorporation of these subunits into the 18-crown-6 framework causes a reduction in conformational flexibility of the chiral cavity and fixes the phenyl chiral barrier perpendicularly above the face of crown ring to modify enantiomer recognition ability. Chiral crown ethers of the 18-crown-6 type were synthesized using these building blocks and their chiral recognition behaviour in differential enantiomer transport through bulk liquid membranes were examined. Chiral azophenolic crown ethers containing cis-1-phenylcyclohexane-1,2-diol or cis-cyclohexane-1,2-diol which can bind neutral amines to form a stable complex and exhibit enantiorecognitive coloration in complexation with chiral amines were prepared and the association constants for their complexes with chiral ethylamine and ethanolamine derivatives were determined on the basis of UV-visible absorbance. The observed enantioselectivity is rationalized in terms of complementarity between a host and a guest as indicated by CPK molecular model examination. The alternation of the position of chiral barriers resulted in a reversal of the enantioselectivity. Crown ethers with diastereotopic faces can bind a guest to each side of the diastereotopic faces to form diastereoisomeric complexes which occasionally cause troublesome ''sidedness'' problems. In order to avoid the problems, most crown ethers previously prepared contained at least one C-2 axis of symmetry. However, diastereotopic face selectivity in complexation does provide helpful information on the complexing behaviour of crown ethers to assist in the design of more elaborate and structured host molecules. meso-Crown ethers having cis-1-phenylcyclohexane-1,2-diol were prepared and the diastereotopic face selectivity by their diastereotopic faces in complexation with achiral amines was examined by temperature-dependent H-1 nuclear magnetic resonance, Ethanolamine is attached stereoselectively to one of the faces to give one of diastereoisomeric complexes and the alternation of the position of steric barriers led to reversal of the diastereotopic face selectivity. A prediction of which diastereoisomeric complex is formed is made on the basis of CPK molecular model.
引用
收藏
页码:199 / 219
页数:21
相关论文
共 53 条
[21]   HOST-GUEST COMPLEXATION 11 SURVEY OF CHIRAL RECOGNITION OF AMINE AND AMINO ESTER SALTS BY DILOCULAR BISDINAPHTHYL HOSTS [J].
KYBA, EP ;
TIMKO, JM ;
KAPLAN, LJ ;
DEJONG, F ;
GOKEL, GW ;
CRAM, DJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (14) :4555-4568
[22]  
LAIDLER DA, 1979, TETRAHEDRON LETT, P465
[23]   STEREOSELECTIVITY IN COMPLEXATION OF PRIMARY ALKYLAMMONIUM CATIONS BY DIASTEREOTOPIC FACES OF CHIRAL ASYMMETRIC CROWNS [J].
LAIDLER, DA ;
STODDART, JF .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (14) :481-483
[24]   ENANTIOMER RECOGNITION OF CROWN ETHERS AND OPEN-CHAIN POLYETHERS CONTAINING THE TRANS-TETRAHYDROFURAN-2,5-DIYLBIS(METHYLENE) SUBUNIT AS THE CHIRAL CENTER [J].
NAEMURA, K ;
EBASHI, I ;
MATSUDA, A ;
CHIKAMATSU, H .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (09) :666-668
[25]   FACILE PREPARATION OF OPTICALLY-ACTIVE BICYCLO[3.3.1]NONANE-2,6-DIOL AND 3,3,7,7-TETRAMETHYLBICYCLO[3.3.1]NONANE-2,6-DIOL BY ENZYME-CATALYZED HYDROLYSIS, AND ENANTIOMER RECOGNITION BEHAVIOR OF CROWN ETHERS AND PODANDS HAVING THESE DIOLS AS A CHIRAL SUBUNIT [J].
NAEMURA, K ;
MATSUMURA, T ;
KOMATSU, M ;
HIROSE, Y ;
CHIKAMATSU, H .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1989, 62 (11) :3523-3530
[26]   THE SYNTHESIS OF AZOPHENOLIC CROWN-ETHERS OF C(S) SYMMETRY INCORPORATING CIS-1-PHENYLCYCLOHEXANE-1,2-DIOL RESIDUES AND DIASTEREOTOPIC FACE SELECTIVITY IN COMPLEXATION OF ETHANOLAMINE BY THEIR DIASTEREOTOPIC FACES [J].
NAEMURA, K ;
TAKEUCHI, S ;
ASADA, M ;
HIROSE, K ;
TOBE, Y ;
KANEDA, T ;
SAKATA, Y .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (06) :711-712
[27]   SYNTHESIS AND ENANTIOMER RECOGNITION OF CROWN ETHERS CONTAINING CYCLOHEXANE-1,2-DIOL DERIVATIVES AS THE CHIRAL CENTER AND ENZYMATIC RESOLUTION OF THE CHIRAL SUBUNITS [J].
NAEMURA, K ;
MIYABE, H ;
SHINGAI, Y .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1991, (04) :957-959
[28]   ENZYMATIC-HYDROLYSIS OF 2,6-DIACETOXYBICYCLO[3.3.1]NONANE AND 2,6-DIACETOXY-3,3,7,7-TETRAMETHYLBICYCLO[3.3.1]NONANE - A FACILE SYNTHESIS OF THE OPTICALLY-ACTIVE CHIRAL SUBUNIT FOR CROWN ETHERS [J].
NAEMURA, K ;
MATSUMURA, T ;
KOMATSU, M ;
HIROSE, Y ;
CHIKAMATSU, H .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (03) :239-241
[29]   PREPARATION AND ENANTIOMER RECOGNITION BEHAVIOR OF CROWN-ETHERS CONTAINING CIS-1-PHENYLCYCLOHEXANE-1,2-DIOL AND TRANS-1,2-DIPHENYLCYCLOHEXANE-1,2-DIOL AS A CHIRAL SUBUNIT [J].
NAEMURA, K ;
MIYABE, H ;
SHINGAI, Y ;
TOBE, Y .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1993, (09) :1073-1077
[30]   SYNTHESIS AND ENANTIOMER RECOGNITION OF DIPODANDS AND CROWN ETHERS CONTAINING THE 2,3-6,7-DIBENZOBICYCLO[3.3.1]NONA-2,6-DIENE RESIDUE AS THE CHIRAL SUBUNIT [J].
NAEMURA, K ;
FUKUNAGA, R ;
KOMATSU, M ;
YAMANAKA, M ;
CHIKAMATSU, H .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1989, 62 (01) :83-88