氨基酸DES催化3-苯基环丁酮的不对称Baeyer-Villiger氧化反应

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文章编号： 1672-6987（2023）02-0013-07； DOI： 10.16351/j.1672-6987.2023.02.002

安健豪a， 于凤丽b*， 解从霞b， 于世涛a（青岛科技大学 a.化工学院; b.化学与分子工程学院，山东 青岛 266042）

摘要： 以手性氨基酸与Brnsted酸为原料合成了一系列新型酸性低共熔溶剂（DES）催化剂，以环境友好的H2O2为氧化剂，首次将DES应用于环酮的不对称Baeyer-Villiger氧化反应中。以3-苯基环丁酮为模板底物，探究了不同DES的催化活性，其中以L-亮氨酸（L-Leu）为氢键受体（HBA）、以H3PO4为氢键供体（HBD）合成的DES为最优催化剂。研究了HBA与HBD的比例、催化剂用量、氧化剂用量、反应温度、反应时间等对催化反应的影响。较佳条件：n(HBD)∶n(HBA)=4∶1,n(DES)∶n（H2O2）∶n（底物）=26∶7∶1，反应温度25 ℃，反应时间5 h。较佳条件下，苯基环丁酮转化率9859%，苯基丁内酯产率7808%，对映体过量百分数6926%。水相中的DES经过干燥后可以重复使用，经过6次循环使用后催化活性有些许下降（DES在每次分离时有少量损失所致）。DES催化剂L-Leu/4H3PO4还可以用于其它环酮底物的B-V氧化反应，结果表明该催化剂具有较好的底物普适性。

关键词： DES催化剂； 不对称Baeyer-Villiger氧化； 苯基环丁酮； 苯基丁内酯

中图分类号： O 643； O 624.4文献标志码： A

引用格式： 安健豪， 于凤丽， 解从霞， 等. 氨基酸DES催化3-苯基环丁酮的不对称

Baeyer-Villiger氧化反应［J］. 青岛科技大学学报(自然科学版), 2023, 44(2): 13-19.

AN Jianhao, YU Fengli, XIE Congxia, et al. Asymmetric Baeyer-Villiger oxidation of phenylcyclobutanone catalyzed by amino acid DES［J］. Journal of Qingdao University of Science and Technology（Natural Science Edition), 2023， 44（2）： 13-19.

Asymmetric Baeyer-Villiger Oxidation of Phenylcyclobutanone

Catalyzed by Amino Acid DES

AN Jianhaoa, YU Fenglib, XIE Congxiab, YU Shitaoa

(a.College of Chemical Engineering; b. College of Chemistry and Molecular Engineering,

Qingdao University of Science and Technology, Qingdao 266042, China)

Abstract: A series of new acidic DES catalysts were synthesized from chiral amino acids and Brnsted acids. Using eco-friendly H2O2 as oxidant, DES catalysts were applied to the asymmetric Baeyer-Villiger catalytic oxidation of cyclobutanones. Using 3-phenylcyclobutanone as template, the catalytic activities of different DESs were investigated, and the best catalyst was DES synthesized with L-Leu as hydrogen bond receptor (HBA) and H3PO4 as hydrogen bond donor (HBD). The effects of the ratio of HBA to HBD, catalyst amount, oxidant dose, reaction temperature, and reaction time on the reaction were studied. The optimum conditions are: n(HBD)∶n(HBA) =4∶1, n(DES)∶n(H2O2)∶n(substrate) =26∶7∶1, reaction temperature 25 ℃, and reaction time 5 h. Under the optimum conditions, the conversion of phenylcyclobutanone is 9859%, the yield of phenylbutyrolactone is 7808%, and ee is 6926%. DES in aqueous phase can be reused after drying, and the catalytic activity decreases slightly after 6 cycles (due to a small loss of DES at each separation). DES catalyst L-Leu/4H3PO4 can also be used for B-V oxidation of other cycloketone substrates, and the results show that DES has good substrate universality.

Key words: DES catalyst; asymmetric Baeyer-Villiger oxidation; phenylcyclobutanone; phenylbutyrolactone

收稿日期： 2022-05-23

基金项目： 国家自然科学基金项目（21878166）；山东省重点研发计划项目（2017GGX70102）．

作者简介： 安健豪（1997—），男，硕士研究生. *通信联系人.