功能化离子液体支载脯氨酸催化的不对称Henry缩合反应

doi:10.3724/SP.J.1095.2014.30480

摘要/Abstract

摘要： 以L-脯氨酸支载在功能化离子液体四氟硼酸1-(2-羟乙基)-3-甲基咪唑鎓盐上的离子液体([Promim]CF3CO2)为催化剂兼溶剂，可在温和条件下顺利地催化硝基乙烷、硝基甲烷和各种醛的Henry缩合反应，目标产物的产率达79％～95％，非对映选择性可达3∶1，对映选择性可达85%ee。反应操作和后处理简单方便。 [Promim]CF3CO2离子液体通过简单的处理即可实现循环利用，以邻-硝基苯甲醛和硝基乙烷为反应底物的模板反应，这种离子液体可以较稳定地循环使用6次，催化活性不降。

关键词: 离子液体支载脯氨酸, Henry缩合反应, 不对称催化

Abstract: A functionalized ionic liquid-supported proline, 1-methyl-3-{2-[(2s)-pyrrolidine-2-carbonyloxy]-ethyl}-1H-imidazol-3-iumtrifluoroacetate([Promim]CF3CO2), was used to catalyze the Henry condensation reaction of aldehydes with CH3CH2NO2 or CH3NO2. The desired products were obtained in 79%~95% yields, diastereomeric excess and enantiomeric excess was up to 3∶1 and 85% under relatively mild conditions. [Promim]CF3CO2 could be efficiently recycled six times without the decrease of catalytic activity in the condensation reaction of 4-nitrobenzaldehyde and CH3CH2NO2.

Key words: ionic liquid-supported proline, Henry condensation, asymmetric catalysis

中图分类号:

O621.2

张宝华, 史兰香. 功能化离子液体支载脯氨酸催化的不对称Henry缩合反应[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30480.

ZHANG Baohua, SHI Lanxiang*. Asymmetric Henry Condensation Catalyzed by Ionic Liquid-supported Proline[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30480.

参考文献

[1] GONG Kai,FANG Dong,SHI Qunrong,et al. Knoevenagel Condensation Reaction Catalyzed by Functionalized Ionic Liquid[J]. Chinese J Appl Chem,2007,24(9):1089-1091(in Chinese).

巩凯，方东，施群荣，等. 碱性功能离子液体催化Knoevenagel缩合反应[J]. 应用化学，2007，24(9)：1089-1091.

[2] David C F,Amanda M L,Doug W M. The Knoevenagel Reaction：Analysis and Recycling of the Ionic Liquid Medium[J]. Tetrahedron Lett,2006,47(11):1699-1703.

[3] Miao W S,Chan T H. Ionic-liquid-supported Organocatalyst:Efficient and Recyclable Ionic-Liquid- Anchored Proline for Asymmetric Aldol reaction[J]. Adv Synth Catal,2006,348(12/13):1711-1718.

[4] Luo S Z,Mi X L,Ahang L,et al. Functionalized Chiral Ionic Liquids as Highly Efficient Asymmetric Organocatalysts for Michael Addition to Nitroolefins[J]. Angew Chem Int Ed,2006,45(19):3093-3097.

[5] Sasai H,Shibasaki M.Catalytic Asymmetric Nitroaldol Reaction：An Efficient Synthesis of (S)-Propranolol Using the Lanthanum Binaphthol Complex[J]. Tetrahedron Lett,1993,34(5):855-858.

[6] Sasai H,Shibasaki M. Syntheses of (S)-(-)-pindolol and [3′-13C]-(R)-(-)-pindolol Utilizing a Lanthanum-lithium-(R)-BINOL [(R)-LLB] Catalyzed Nitroaldol Reaction[J]. Tetrahedron,1994,50(43):12313-12318.

[7] Takaoka E,Shibasaki M. Catalytic Asymmetric Synthesis of Arbutamine[J]. Hereocycles,1997,46:157-163

[8] Corey E J,Zhang F Y. Re- and Si-face-selective Nitroaidol Reactions Catalyzed by a Rigid Chiral Quaternary Ammonium Salt: a Highly Stereo-selective Synthesis of the HIV Protease Inhibitor Amprenavir(Vertex 478)[J]. Angew Chem Int Ed,1999,38(13/14):1931-1933.

[9] Chen Z,Li Y,Xie H,et al. Ionic-liquid-supported Proline as a Catalyst for Direct Asymmetric Aldol Reaction[J]. Russ J Org Chem,2008,44(12): 1807-1810.

[10] CHEN Xuewei,LI Xuehui,SONG Hongbing,et al. Synthesis of a Basic Imidazolide Ionic Liquid and Its Application in Catalyzing Knoevenagel Condensation[J]. Chinese J Catal,2008,29(10):957-959 (in Chinese).

陈学伟，李雪辉，宋红兵，等. 咪唑阴离子型碱性离子液体的合成及其催化Knoevenagel缩合反应[J]. 催化学报，2008，29(10)：957-959.