Abidi S L
U.S. Fish and Wildlife Service, National Fishery Research Center, La Crosse, WI 54602-0818.
J Chromatogr. 1987 Aug 28;404(1):133-43. doi: 10.1016/s0021-9673(01)86844-8.
The high-performance liquid chromatographic (HPLC) behavior of parent rotenoids (type I) and the hydroxy-analogues (type II) on three different chiral stationary phases (CSPs) was studied. Separations of optical isomers were achieved in various degrees depending largely upon the rotenoidal structures and the CSP types employed. Enantiomers of all but elliptone compounds were separable on beta-cyclodextrin-bonded silica (CDS). Without exception, the 12a-hydroxyrotenoid antipodes were resolved on Pirkle's phenylglycine-bonded silica (PGS) despite unsuccessful attempts to resolve the type I rotenoidal racemates. Conversely, optical resolution of the latter rotenoids was accomplished by using a helical polytriphenylmethylacrylate-coated silica (TPS) column and the observed separation factors (alpha values) ranged from 1.14 to 1.90. The results from HPLC of type II rotenoids on TPS (alpha = 1.00-1.63) suggested that variations in E-ring structures had profound influence on the resolution outcome. Conjugated double bonds on the E-ring and the desisopropylation of the five-membered E-ring of type II rotenoids appeared to be important structural features for chiral recognition involving the TPS substrate. In both reversed-phase (CDS) and normal-phase (PGS and TPS) HPLC modes, the less polar enantiomers were the 6a beta,12a beta-rotenoids as observed in most cases, though this relationship was reversed in the cases of deguelin and hydroxyelliptone probably due to conformational effects of rotenoidal ring systems.
研究了母体鱼藤酮类化合物（I型）及其羟基类似物（II型）在三种不同手性固定相（CSP）上的高效液相色谱（HPLC）行为。光学异构体的分离程度各不相同，这在很大程度上取决于鱼藤酮类化合物的结构和所使用的CSP类型。除椭圆酮化合物外，所有对映体在β-环糊精键合硅胶（CDS）上均可分离。无一例外，尽管未能成功拆分I型鱼藤酮类外消旋体，但12a-羟基鱼藤酮类对映体在Pirkle苯基甘氨酸键合硅胶（PGS）上得以拆分。相反，使用螺旋状聚三苯基甲基丙烯酸酯涂覆硅胶（TPS）柱实现了后一类鱼藤酮类化合物的光学拆分，观察到的分离因子（α值）范围为1.14至1.90。II型鱼藤酮类化合物在TPS上的HPLC结果（α = 1.00 - 1.63）表明，E环结构的变化对拆分结果有深远影响。II型鱼藤酮类化合物E环上的共轭双键和五元E环的去异丙基化似乎是涉及TPS底物的手性识别的重要结构特征。在反相（CDS）和正相（PGS和TPS）HPLC模式下，在大多数情况下，极性较小的对映体是6aβ,12aβ-鱼藤酮类化合物，不过在鱼藤素和羟基椭圆酮的情况下，这种关系可能由于鱼藤酮类环系统的构象效应而相反。
