含苯环β-环糊精衍生物自包结对反应对映选择性的影响

化工进展

含苯环β-环糊精衍生物自包结对反应对映选择性的影响

孙吉龙1，姚兴东1，沈海民2，纪红兵1，2

1广西民族大学化学与化工学院，广西南宁 530006；2中山大学化学与化学工程学院，广东广州 510275

出版日期:2013-12-05 发布日期:2013-12-05

Effect of self-inclusion of β-cyclodextrin derivatives with phenyl group on enantioselectivity for oxidation of thioanisole by H2O2

SUN Jilong1，YAO Xingdong1，SHEN Haimin2，JI Hongbing1，2

1School of Chemistry and Chemical Engineering，Guangxi University for Nationalities，Nanning 530006，Guangxi，China；2School of Chemistry and Chemical Engineering，Sun Yat-sen University，Guangzhou 510275，Guangdong，China

Online:2013-12-05 Published:2013-12-05

摘要/Abstract

摘要： 以单(6-O-p-甲苯磺酰基)-β-环糊精为反应原料，通过亲核取代合成了3个带苯环的β-环糊精衍生物CD-1～CD-3，收率为9.93%～17.51%，衍生物的结构通过1H NMR和ESI-MS进行了表征确认。将合成的β-环糊精衍生物与Na2MoO4?2H2O络合后应用于催化H2O2氧化苯甲硫醚。结果表明，反应介质的pH值对该反应体系的收率有一定影响。通过1H ROESY NMR发现，CD-1～CD-3的分子内自包结是影响Na2MoO4?2H2O催化氧化苯甲硫醚不对称反应产物ee%值的主要原因。通过量子化学计算对自包结状态进行了证实。

关键词: 环糊精衍生物, 自包结, 量子化学计算

Abstract: Three β-cyclodextrin derivatives CD-1 to CD-3 were synthesized via nucleophilic substitution of mono (6-O-toluenesulfonyl)-β-cyclodextrin in the yield of 9.93% to 17.51%. All the β-cyclodextrin derivatives were characterized by 1H NMR and ESI-MS. The β-cyclodextrin derivatives CD-1～CD-3 coordinated with Na2MoO4?2H2O，and the product was used for catalytic oxidation of thioanisole by H2O2. The yield of the reaction was influenced by reaction medium and pH of the reaction system. Asymmetric oxidation of thioanisole by Na2MoO4?2H2O was induced by β-cyclodextrin derivatives. 1H ROESY NMR characterization showed that intramolecular self-inclusion of CD-1～CD-3 was the main factor limiting the ee% values of the product. The result was verified by quantum chemistry calculation.

Key words: cyclodextrin derivatives, self-inclusion, quantum chemistry calculation

孙吉龙1，姚兴东1，沈海民2，纪红兵1，2. 含苯环β-环糊精衍生物自包结对反应对映选择性的影响[J]. 化工进展.

SUN Jilong1，YAO Xingdong1，SHEN Haimin2，JI Hongbing1，2. Effect of self-inclusion of β-cyclodextrin derivatives with phenyl group on enantioselectivity for oxidation of thioanisole by H2O2[J]. Chemical Industry and Engineering Progree.