β-环糊精衍生物诱导H2O2水相不对称环氧化trans-查尔酮
收稿日期: 2015-12-17
修回日期: 2016-02-19
网络出版日期: 2016-04-05
基金资助
国家杰出青年科学基金（No. 21425627）资助项目.
Asymmetric Epoxidation of trans-Chalcone by H2O2 Induced by β-Cyclodextrin Derivatives in Water
Received date: 2015-12-17
Revised date: 2016-02-19
Online published: 2016-04-05
Supported by
Project supported by the National Science Fund for Distinguished Young Scholars (No. 21425627).
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H2O2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H2O2与NaHCO3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.
朱庆英 , 沈海民 , 纪红兵 . β-环糊精衍生物诱导H2O2水相不对称环氧化trans-查尔酮[J]. 有机化学, 2016 , 36(8) : 1907 -1914 . DOI: 10.6023/cjoc201512022
Six amino-alcohol modified β-cyclodextrins CD-1～CD-6 were synthesized by nucleophilic substitution from mono(6-O-p-tolylsulfonyl)-β-cyclodextrin with the yields of 34%～58%, and were verified by 1H NMR, 13C NMR and ESI-MS techniques. These β-cyclodextrin derivatives were applied to the asymmetric epoxidation of trans-chalcone by H2O2. And the results implied that the dosage of the β-cyclodextrin derivatives and the structure of the modified group had an important effect on the enantioselectivity in the reaction. Among them, CD-1 exhibited the best performance in the asymmetric epoxidation of trans-chalcone employed H2O2 and NaHCO3 as oxidant, and 25.7% ee value was obtained. It were showed from the spectra of 2D-1H ROESY NMR that, CD-1 could form inclusion complex with trans-chalcone and self-inclusion existed in all the β-cyclodextrin derivatives CD-1～CD-6, which affected the enhancement of the ee value. And the two kinds of inclusion complexes were confirmed by quantum chemistry calculation too.
Key words： β-cyclodextrin; asymmetry; epoxidation; trans-chalcone
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