AN OPTIMIZED SEQUENTIAL KINETIC RESOLUTION OF TRANS-1,2-CYCLOHEXANEDIOL

被引:30
作者
CARON, G [1 ]
KAZLAUSKAS, RJ [1 ]
机构
[1] MCGILL UNIV,DEPT CHEM,801 SHERBROOKE ST W,MONTREAL H3A 2K6,QUEBEC,CANADA
关键词
D O I
10.1021/jo00026a014
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Quantitative analysis of sequential kinetic resolutions (resolutions that proceed via two or more enantioselective steps) indicates that optimal reinforcement of the enantioselectivities occurs when the rates of the two steps are equal. Under these conditions, the reinforcement is multiplicative and the overall enantioselectivity, E(T(max)), is given approximately by [1 + (E1E2)]/2. To test these ideas we optimized the resolution of trans-1,2-cyclohexanediol, 1. The first step of the porcine liver esterase (PLE) catalyzed hydrolysis of trans-1,2-diacetoxycyclohexane proceeded 47 times faster than the second step and the resolution yielded 1 with only 58% ee at 44 mol %. Addition of a hexane phase slowed the first step by selectively extracting the fast-reacting 1-diacetate (relative rate = 6) and increased the enantiomeric purity to 94% ee at 34 mol %. The resolution of 1 was further improved using lipase from Pseudomonas cepacia (Amano P, PCL) which showed an E(T(max)) of > 2000 as compared to an E(T(max)) for PLE of 54. Resolution with PCL after equalization of the rates of the two steps gave (R)-1 and recovered (S)-1-diacetate both with > 99% ee.
引用
收藏
页码:7251 / 7256
页数:6
相关论文
共 31 条
[1]  
ANCHISI C, 1983, GAZZ CHIM ITAL, V113, P73
[2]   QUANTITATIVE-ANALYSES OF BIOCHEMICAL KINETIC RESOLUTIONS OF ENANTIOMERS [J].
CHEN, CS ;
FUJIMOTO, Y ;
GIRDAUKAS, G ;
SIH, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (25) :7294-7299
[3]   ENZYMATIC-HYDROLYSIS OF (+/-)-TRANS-1,2-DIACETOXYCYCLOALKANES - A FACILE ROUTE TO OPTICALLY-ACTIVE CYCLOALKANE-1,2-DIOLS [J].
CROUT, DHG ;
GAUDET, VSB ;
LAUMEN, K ;
SCHNEIDER, MP .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (10) :808-810
[4]   ENZYMES IN ORGANIC-SYNTHESIS .3. SYNTHESIS OF ENANTIOMERICALLY PURE PROSTAGLANDIN INTERMEDIATES BY ENZYME-CATALYZED TRANS-ESTERIFICATION OF (1SR,2RS,5SR,6RS)-BICYCLO[3.3.0]OCTANE-2,6-DIOL WITH TRICHLOROETHYL ACETATE IN AN ORGANIC-SOLVENT [J].
DJADCHENKO, MA ;
PIVNITSKY, KK ;
THEIL, F ;
SCHICK, H .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1989, (11) :2001-2002
[5]   CHIRAL ALCOHOL-INDUCED DIASTEREOSELECTIVE CONJUGATE ADDITION AND CYCLIZATION [J].
FANG, CL ;
SUEMUNE, H ;
SAKAI, K .
TETRAHEDRON LETTERS, 1990, 31 (33) :4751-4754
[6]   SYNTHESIS OF ALPHA-AMINO-ACIDS .1. SCHIFF-BASE OF GLYCINE METHYL-ESTER - A NEW AND EFFICIENT PROCHIRAL NUCLEOPHILE IN PALLADIUM CHIRAL CATALYTIC ALLYLATION [J].
GENET, JP ;
FERROUD, D ;
JUGE, S ;
MONTES, JR .
TETRAHEDRON LETTERS, 1986, 27 (38) :4573-4576
[7]   SEQUENTIAL BIOCATALYTIC KINETIC RESOLUTIONS [J].
GUO, ZW ;
WU, SH ;
CHEN, CS ;
GIRDAUKAS, G ;
SIH, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (12) :4942-4945
[8]  
HASSNER A, 1978, TETRAHEDRON LETT, P4475
[9]   THE ASYMMETRIC HYDROCARBOALKOXYLATION OF OLEFINS CATALYZED BY PALLADIUM CHIRAL BIS(DIBENZOPHOSPHOLE) COMPLEXES [J].
HAYASHI, T ;
TANAKA, M ;
OGATA, I .
JOURNAL OF MOLECULAR CATALYSIS, 1984, 26 (01) :17-30
[10]   CHIRAL CROWN ETHERS DERIVED FROM (+)-(1S, 2S)-TRANS-CYCLOHEXANE-1,2-DIOL [J].
HAYWARD, RC ;
OVERTON, CH ;
WHITHAM, GH .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1976, (22) :2413-2415