STEREOCHEMICAL ASPECTS OF CYTOSOLIC EPOXIDE HYDROLASE HYDRATION OF METHYL DIEPOXYSTEARATES

被引:16
作者
BORHAN, B
NOUROOZZADEH, J
UEMATSU, T
HAMMOCK, BD
KURTH, MJ
机构
[1] UNIV CALIF DAVIS,DEPT CHEM,DAVIS,CA 95616
[2] UNIV CALIF DAVIS,DEPT ENTOMOL,DAVIS,CA 95616
[3] UNIV CALIF DAVIS,DEPT ENVIRONM TOXICOL,DAVIS,CA 95616
基金
美国国家卫生研究院;
关键词
D O I
10.1016/S0040-4020(01)86339-0
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Hydration of methyl diepoxystearate (2) al high cytosolic epoxide hydrolase (CEH) concentration produces the corresponding tetraol, while al physiological CEH concentration four tetrahydrofuran diol products (3-6) are produced. These same four products are obtained in the acid-catalyzed hydration of 2. Spectroscopic studies, primarily EI mass spectrometry and difference spectrum NOE, are reported which establish the regio- and stereoselectivity of 2 --> 3-6 (MS differentiating 3/4 from 5/6 and NOE differentiating 315 from 4/6). The observed syn arrangement of the two adjacent groups (i.e., substituents at C2 and C3) in the four THF-diols can only arise from an A2 type opening of the first epoxide. The resulting epoxydiol intermediate then cyclizes by A2 opening of the second cis-epoxide as established by synthesis of these hypothetical epoxydiol intermediates and their subsequent conversion to THF-diols 3-6.
引用
收藏
页码:2601 / 2612
页数:12
相关论文
共 24 条
[1]   ANOMALOUS STERIC COURSE OF RING-OPENING REACTIONS OF INDENE OXIDE - RE-EXAMINATION [J].
BALSAMO, A ;
BERTI, G ;
CROTTI, P ;
FERRETTI, M ;
MACCHIA, B ;
MACCHIA, F .
JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (17) :2596-2598
[2]   NADPH-DEPENDENT MICROSOMAL METABOLISM OF 14, 15-EPOXYEICOSATRIENOIC ACID TO DIEPOXIDES AND EPOXYALCOHOLS [J].
CAPDEVILA, JH ;
MOSSET, P ;
YADAGIRI, P ;
LUMIN, S ;
FALCK, JR .
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1988, 261 (01) :122-133
[3]   EPOXY DERIVATIVES OF ARACHIDONIC-ACID ARE POTENT STIMULATORS OF PROLACTIN SECRETION [J].
CASHMAN, JR ;
HANKS, D ;
WEINER, RI .
NEUROENDOCRINOLOGY, 1987, 46 (03) :246-251
[4]   THE EFFECT OF HEPATIC-MICROSOMAL AND CYTOSOLIC SUBCELLULAR-FRACTIONS ON THE MUTAGENIC ACTIVITY OF EPOXIDE-CONTAINING COMPOUNDS IN THE SALMONELLA ASSAY [J].
ELTANTAWY, MA ;
HAMMOCK, BD .
MUTATION RESEARCH, 1980, 79 (01) :59-71
[5]   SUBSTITUENT EFFECTS ON RATES AND PRODUCT DISTRIBUTIONS IN THE HYDROLYSIS REACTIONS OF NAPHTHALENE TETRAHYDRO EPOXIDES - MODELS FOR TETRAHYDRO EPOXIDES OF POLYCYCLIC AROMATIC-HYDROCARBONS [J].
GILLILAN, RE ;
POHL, TM ;
WHALEN, DL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (16) :4481-4482
[6]   CATABOLISM OF EPOXY FATTY ESTERS BY THE PURIFIED EPOXIDE HYDROLASE FROM MOUSE AND HUMAN-LIVER [J].
HALARNKAR, PP ;
WIXTROM, RN ;
SILVA, MH ;
HAMMOCK, BD .
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1989, 272 (01) :226-236
[7]   SYMMETRY-ASSISTED SYNTHESIS OF TRIEPOXIDE STEREOISOMERS OF (E,Z,E)-DODECA-2,6,10-TRIENE-1,12-DIOL AND THEIR CASCADE REACTIONS TO 2,5-LINKED BISTETRAHYDROFURANS [J].
HOYE, TR ;
SUHADOLNIK, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (18) :5312-5313
[8]   STEREOCONTROLLED SYNTHESIS OF 2,5-LINKED BISTETRAHYDROFURANS VIA THE TRIEPOXIDE CASCADE REACTION [J].
HOYE, TR ;
SUHADOLNIK, JC .
TETRAHEDRON, 1986, 42 (11) :2855-2862
[9]   HYDROLYSIS OF SUBSTITUTED ETHYLENE OXIDES IN H2O18 SOLUTIONS [J].
LONG, FA ;
PRITCHARD, JG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1956, 78 (12) :2663-2667
[10]  
MANSON MM, 1980, BRIT J IND MED, V37, P317