Absolute configurations of K-region epoxide enantiomers of 3-methylcholanthrene, benz[a]anthracene, and benzo[a]pyrene.
Absolute configurations of K-region epoxide enantiomers of 3-methylcholanthrene, benz[a]anthracene, and benzo[a]pyrene.
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3-甲基胆蒽、苯并[a]蒽和苯并[a]芘的K区环氧化物对映体的绝对构型。
DOI：
10.1021/ac00149a011
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发表时间：
1987
影响因子：
7.4
通讯作者：
Yang,SK
中科院分区：
文献类型：
--
作者：
Weems,HB;Mushtaq,M;Yang,SK
通过它们的单甲醚衍生物测定了3-甲基蒽、苯并[a]-蒽和苯并[a]-芘的k -环氧环龙对映体的绝对构型。每一种环氧化合物外消旋体或对映体经甲氧基醇钠分离得到一对单甲基醚衍生物，用正相高效液相色谱法分离得到。甲氧基的位置由酸催化脱水和/或去甲醇化形成的产物决定。每个环氧化物及其甲氧基化衍生物的对映异构体在本研究中使用的四个Plrkle手性固定相高效液相色谱柱中至少有两个被分离。通过与已知绝对构型的反式羟基对映体衍生的对映体单甲基醚衍生物的圆光谱比较，建立了对映体单甲基醚衍生物的绝对溶质立体化学。由甲氧基的位置和对映单甲醚衍生物的绝对构型推导出各环氧化物对映体的绝对构型。结果表明，该方法一般适用于多环芳烃环氧k -雷龙对映体绝对构型的测定。环氧化合物（芳烃氧化物）是哺乳动物细胞色素p -450同工酶代谢多环芳烃（PAHs）的主要初始产物（1,2）。虽然一些多环芳烃环氧化物具有致突变和/或细胞毒性活性（1,2），但其他多环芳烃环氧化物被进一步代谢为无毒或致突变和致癌产物（3,4）。微粒体细胞色素P-450同工酶和环氧化物水解酶的立体选择性解释了光学活性环氧化物、二氢二醇和二氢二醇环氧化物的形成，其中一些是一些多环芳烃的近似和最终致癌代谢物（3-6）。
The absolute configurations of K-reglon epoxide enantiomers of 3-methylcholanthrene, benz [a Janthracene, and benzo [a]-pyrene have been determined via their monomethyl ether derivatives. Methoxylatlon of each racemic or enantiomeric epoxide by sodium methoxlde resulted In a pair of mono-methyl ether derivatives, which were separated by normal-phase high-performance liquid chromatography (HPLC). The position of the methoxy group was determined by products formed by acid-catalyzed dehydration and/or demethanolization of each monomethyl ether derivative. En-antiomers of each epoxide and Its methoxylated derivatives were resolved by at least two of the four Plrkle chiral stationary phase HPLC columns utilized In this study. The ab-solute stereochemistries of enantiomeric monomethyl ether derivatives were established by comparing their circular dlchrolsm spectra with those of enantiomeric monomethyl ether derivatives derived from trans dlhydrodlol enantiomers of known absolute configurations. The absolute configuration of each epoxide enantiomer was deduced from the location of the methoxy group and the absolute configuration of enan-tiomeric monomethyl ether derivatives. Results Indicate that the method described Is useful In general for the determination of absolute configurations of K-reglon epoxide enantiomers of polycyclic aromatic hydrocarbons.Epoxides (arene oxides) are major initial products formed in the metabolism of polycyclic aromatic hydrocarbons (PAHs) by mammalian cytochrome P-450isozymes (1, 2). While some PAH epoxides possess mutagenic and/or cytotoxic activities (1, 2), others are further metabolized either to nontoxic or to mutagenic and carcinogenic products (3, 4). The stereoselective natures of microsomal cytochrome P-450 isozymes and epoxide hydrolase account for theformation of optically active epoxides, dihydrodiols, and dihydrodiol epoxides, some of which are proximate and ultimate carcinogenic metabolites of some PAHs (3-6).