手性类卟啉N4配体与锰络合物氧化动力学拆分消旋芳香环亚砜

doi:10.6023/cjoc201805034

有机化学 ›› 2018, Vol. 38 ›› Issue (11): 3070-3077.DOI: 10.6023/cjoc201805034 上一篇下一篇

研究论文

手性类卟啉N4配体与锰络合物氧化动力学拆分消旋芳香环亚砜

杨金闯^a,b, 李国松^b, 吕成伟^a, 安悦^a, 高爽^b

a 辽宁师范大学化学化工学院大连 116029;
b 中国科学院大连化学物理研究所国家清洁能源实验室大连 116023

收稿日期:2018-05-16 修回日期:2018-06-19 发布日期:2018-07-05
通讯作者: 安悦, 高爽 E-mail:anyue_11@163.com;sgao@dicp.ac.cn
基金资助:
国家自然科学基金（No.21403100）、辽宁省教育厅高等教育研究基金（No.L2014421）资助项目.

Oxidation Kinetics Resolution of Racemic Aromatic Sulfoxides by Chiral Porphyrin-Inspired N4 Ligand with Manganese Complex

Yang Jinchuang^a,b, Li Guosong^b, Lü Chengwei^a, An Yue^a, Gao Shuang^b

a Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023;
b College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029

Received:2018-05-16 Revised:2018-06-19 Published:2018-07-05
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21403100) and the Education Research Program of the Education Department of Liaoning Province (No. L2014421).

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1. 手性类卟啉N4配体与锰络合物氧化动力学拆分消旋芳香环亚砜.PDF(924KB)

摘要/Abstract

以手性类卟啉N₄配体与金属锰原位络合化合物作为催化剂，环境友好型氧源H₂O₂作为氧化剂，金刚烷甲酸作为添加剂，对消旋芳香环亚砜进行了氧化动力学拆分.应用该催化体系对芳基烷基和芳基苄基类亚砜底物进行拓展，最高可获得手性亚砜产率为40%，对映体选择性为100%.与此同时，亚砜的进一步氧化产物砜的产率最高可达到72%.通过富电子亚砜与缺电子亚砜底物的竞争实验，发现此催化氧化体系更倾向于富电子亚砜.另外，克级规模的氧化动力学拆分的成功也说明了此类拆分方法在方法学上具有一定的实际应用价值.

关键词: N₄配体, 锰, 氧化动力学拆分, 芳基亚砜, 砜

Oxidative kinetics resolution of racemic aromatic sulfoxide was studied by using chiral porphyrin-inspired N₄ ligands and manganese in situ complex as catalyst, environment-friendly H₂O₂ as oxidant and adamantanecarboxylic acid as additive. The arylalkyl and arylbenzyl sulfoxide substrates were extended by this catalytic system. A maximum yield of chiral sulfoxide was 40% and the enantioselectivity was 100%. In the meantime, the yield of sulfone a further oxidation products of sulfoxide, was up to 72%. It was found that the catalytic oxidation system is more prone to electron-rich sulfoxide through the competition experiment between electron-rich sulfoxide and electron-deficient sulfoxide substrates. In addition, the success of gram-scale oxidation kinetic resolution also shows that this method has a certain practical value in methodology.

Key words: ligand N₄, manganese, oxidative kinetic resolution, aromatic sulfoxides, sulfone

引用此文

杨金闯, 李国松, 吕成伟, 安悦, 高爽. 手性类卟啉N4配体与锰络合物氧化动力学拆分消旋芳香环亚砜[J]. 有机化学, 2018, 38(11): 3070-3077.

Yang Jinchuang, Li Guosong, Lü Chengwei, An Yue, Gao Shuang. Oxidation Kinetics Resolution of Racemic Aromatic Sulfoxides by Chiral Porphyrin-Inspired N4 Ligand with Manganese Complex[J]. Chin. J. Org. Chem., 2018, 38(11): 3070-3077.

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手性类卟啉N4配体与锰络合物氧化动力学拆分消旋芳香环亚砜

Oxidation Kinetics Resolution of Racemic Aromatic Sulfoxides by Chiral Porphyrin-Inspired N4 Ligand with Manganese Complex

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