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以单(6-O-对甲苯磺酰基)-β-环糊精为原料,经亲核取代反应合成了氨基醇修饰的β-环糊精衍生物CD-1~CD-6,收率在34%~58%,结构通过1H NMR,13C NMR和ESI-MS表征确认.将β-环糊精衍生物CD-1~CD-6应用于诱导水相H_2O_2不对称环氧化trans-查尔酮,研究结果表明,β-环糊精衍生物的量和修饰基团结构对该反应体系的对映选择性有较大影响.其中,β-环糊精衍生物CD-1在诱导H_2O_2与Na HCO_3组合水相不对称环氧化trans-查尔酮中效果最佳,ee值达到25.7%.通过2D-1H ROESY NMR表征发现,trans-查尔酮和CD-1之间可以形成包结络合物,同时CD-1~CD-6均存在着修饰基团的自包结行为,影响产物ee值的提高,这两种包结形式均通过量子化学计算得到了映证.
Amino-alcohol-modified β-cyclodextrin derivative CD-1 ~ CD-6 was synthesized by nucleophilic substitution using mono (6-O-tosyl) -β-cyclodextrin as starting material in a yield of The structures were confirmed by 1H NMR, 13C NMR and ESI-MS. CD-1 ~ CD-6 derivatives were used to induce the asymmetric epoxidation of H_2O_2 in aqueous solution trans- Ketone, the results show that the amount of β-cyclodextrin derivatives and the structure of the modified group have a significant impact on the enantioselectivity of the reaction system, in which β-cyclodextrin derivative CD-1 in the induction of H 2 O 2 and The results showed that the ee value reached 25.7% with the asymmetric epoxidation of trans-Chalcone by Na HCO 3, and the inclusion of trans-Chalcone and CD-1 could be formed by 2D-1H ROESY NMR characterization At the same time, the self-enciphering behavior of the modified groups existed in CD-1 ~ CD-6, and the ee value of the product increased. Both of the two kinds of inclusion forms were mapped by quantum chemistry calculation.