Asymmetric Oxidation of Thioanisole with H2O2 Catalyzed by Na2MoO4 and Induced by β-Cyclodextrin Derivatives

doi:10.6023/cjoc1202202

Chin. J. Org. Chem. ›› 2012, Vol. 32 ›› Issue (9): 1684-1689.DOI: 10.6023/cjoc1202202 Previous Articles Next Articles

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β-环糊精衍生物诱导Na₂MoO₄催化H₂O₂不对称氧化苯甲硫醚

沈海民, 纪红兵

中山大学化学与化学工程学院广州 510275

收稿日期:2012-02-20 修回日期:2012-05-21 发布日期:2012-04-13
通讯作者: 纪红兵 E-mail:jihb@mail.sysu.edu.cn
基金资助:
国家自然科学基金(Nos.21176268, 21036009)、2010 年广东省高等学校高层次人才、中央高校基本科研业务费专项资金资助项目

Asymmetric Oxidation of Thioanisole with H₂O₂ Catalyzed by Na₂MoO₄ and Induced by β-Cyclodextrin Derivatives

Shen Hai-Min, Ji Hong-Bing

School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275

Received:2012-02-20 Revised:2012-05-21 Published:2012-04-13
Supported by:
Project supported by the National Natural Science Foundation of China (Nos.21176268, 21036009), the Higher-Level Talent Project for Guangdong Provincial Universities in 2010 and the Fundamental Research Funds for the Central Universities

Five new cycloamino-alcohol modified β-cyclodextrins CD-1～CD-5 were synthesized via nucleophilic substitution from mono(6-O-p-tolylsulfonyl)-β-cyclodextrin in the yields of 36%～68%, and were characterized by ¹H NMR,¹³C NMR and ESI-MS techniques. Then these β-cyclodextrin derivatives were applied to the asymmetric oxidation of thioanisole as the ligand of Na₂MoO₄ using H₂O₂ as oxidant. It was demonstrated that the pH value of the reaction medium presented an important effect on the enantioselectivity in this reaction system. For the better one, CD-4, in aqueous CH₃COONa-HCl buffer solution (pH 7.0), 21.25% ee value was obtained in the asymmetric oxidation of thioanisole with H₂O₂ catalyzed by Na₂MoO₄. The result of 2D-¹H ROESY NMR demonstrated that the origin of the low ee value was the self-inclusion of CD-1～CD-5 in the asymmetric oxidation of thioanisole, which was also confirmed by quantum calculation.

Key words: cyclodextrin, asymmetry, oxidation, thioanisole, self-inclusion

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Shen Hai-Min, Ji Hong-Bing. Asymmetric Oxidation of Thioanisole with H₂O₂ Catalyzed by Na₂MoO₄ and Induced by β-Cyclodextrin Derivatives[J]. Chin. J. Org. Chem., 2012, 32(9): 1684-1689.

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β-环糊精衍生物诱导Na₂MoO₄催化H₂O₂不对称氧化苯甲硫醚

Asymmetric Oxidation of Thioanisole with H₂O₂ Catalyzed by Na₂MoO₄ and Induced by β-Cyclodextrin Derivatives

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β-环糊精衍生物诱导Na2MoO4催化H2O2不对称氧化苯甲硫醚