Schumacher Douglas D, Mitchell Clifford R, Xiao Tom L, Rozhkov Roman V, Larock Richard C, Armstrong Daniel W
Department of Chemistry, Iowa State University, Ames, IA 50011, USA.
J Chromatogr A. 2003 Sep 5;1011(1-2):37-47. doi: 10.1016/s0021-9673(03)01128-2.
A set of 28 racemic dihydrofurocoumarins in which the stereogenic center is located in the furan ring have been synthesized. Currently no effective asymmetric synthesis of this class of compounds exists, although their enantiomers are produced biologically by certain plants. Their diverse medicinal properties are being investigated in several laboratories. The enantioselective separation of these dihydrofurocoumarins by three native and six derivatized cyclodextrins has been evaluated in the reversed-phase mode, the polar organic mode, and normal-phase mode. The hydroxypropyl-beta-cyclodextrin is the most effective chiral stationary phase (CSP) at separating the dihydrofurocoumarins into enantiomers, showing some enantioselectivity for 22 dihydrofurocoumarins, and baseline resolving 16 of the 28 compounds in the reversed-phase mode. The acetyl-beta-cyclodextrin and 2,3-dimethyl-beta-cyclodextrin also showed enantioselectivity for a large number (18 and 17, respectively) of dihydrofurocoumarins in the reversed-phase mode. The native cyclodextrins are ineffective and the aromatic derivatized beta-cyclodextrins are only marginally effective at separating the furocoumarin enantiomers in the reversed-phase mode. The polar organic mode and the normal-phase mode have also been evaluated with these CSPs, but no enantioseparations were observed.
已经合成了一组28种外消旋二氢呋喃香豆素，其中手性中心位于呋喃环中。目前，这类化合物尚无有效的不对称合成方法，尽管它们的对映体是由某些植物生物合成的。几个实验室正在研究它们多样的药用特性。通过三种天然环糊精和六种衍生化环糊精，在反相模式、极性有机模式和正相模式下，对这些二氢呋喃香豆素进行了对映体选择性分离评估。羟丙基-β-环糊精是将二氢呋喃香豆素分离为对映体最有效的手性固定相（CSP），对22种二氢呋喃香豆素表现出一定的对映体选择性，并在反相模式下基线分离了28种化合物中的16种。乙酰基-β-环糊精和2,3-二甲基-β-环糊精在反相模式下对大量（分别为18种和17种）二氢呋喃香豆素也表现出对映体选择性。天然环糊精无效，芳香族衍生化的β-环糊精在反相模式下分离呋喃香豆素对映体的效果也很有限。也用这些CSP对极性有机模式和正相模式进行了评估，但未观察到对映体分离。
