Cesium Carbonate Catalyzed Aza-Michael Addition of Pyrazole to α,β-Unsaturated Ketones

doi:10.6023/cjoc201406051

Chin. J. Org. Chem. ›› 2015, Vol. 35 ›› Issue (1): 121-128.DOI: 10.6023/cjoc201406051 Previous Articles Next Articles

Articles

碳酸铯催化吡唑与α,β-不饱和酮的氮杂Michael反应

杨靖亚^a, 马奔^a, 周红艳^b, 占宝华^a, 李政^a

a 西北师范大学化学化工学院兰州 730070;
b 甘肃农业大学理学院兰州 730070

收稿日期:2014-06-30 修回日期:2014-09-24 发布日期:2014-10-09
通讯作者: 杨靖亚 E-mail:yangjy@nwnu.edu.cn
基金资助:
国家自然科学基金(Nos. 21362034, 21162026)、高等学校博士学科点专项科研基金(No. 20136203120005)、甘肃省自然科学基金(No. 1107RJZ189)、西北师范大学青年教师科研能力提升计划(No. NWNU-LKQN-11-15)和甘肃农业大学科技创新基金(No. GAU-CX1115)资助项目.

Cesium Carbonate Catalyzed Aza-Michael Addition of Pyrazole to α,β-Unsaturated Ketones

Yang Jingya^a, Ma Ben^a, Zhou Hongyan^b, Zhan Baohua^a, Li Zheng^a

a College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070;
b College of Science, Gansu Agricultural University, Lanzhou 730070

Received:2014-06-30 Revised:2014-09-24 Published:2014-10-09
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21362034, 21162026), the Research Fund for the Doctoral Program of Higher Education of China (No. 20136203120005), the Provincial Natural Science Foundation of Gansu Province (No. 1107RJZ189), the Program for Improving Scientific Research Ability of Young Teachers of Northwest Normal University (No. NWNU-LKQN-11-15) and the Science and Technology Innovation Fund of Gansu Agricultural University (No. GAU-CX1115).

1. Cesium Carbonate Catalyzed Aza-Michael Addition of Pyrazole to α,β-Unsaturated Ketones.PDF(2635KB)

Abstract

A Cs₂CO₃-catalyzed aza-Michael reaction of pyrazole to α,β-unsaturated ketones has been developed. With 5 mol% Cs₂CO₃ as catalyst, a series of β-N1-pyrazoly ketones were achieved in 86%～95% yields after 7～12 h in refluxing dioxane. Both aromatic and aliphatic α,β-unsaturated ketones as well as methacrylate and nitrostyrene are well tolerated. Broad scope of substrate and easily scale up make this protocol really practical. Furthermore, the product could be facilely transformed into corresponding γ-amino alcohol.

Key words: Michael addition, nitrogen heterocycles, α,β-unsaturated ketones, catalysis, cesium carbonate

Cite this article

Yang Jingya, Ma Ben, Zhou Hongyan, Zhan Baohua, Li Zheng. Cesium Carbonate Catalyzed Aza-Michael Addition of Pyrazole to α,β-Unsaturated Ketones[J]. Chin. J. Org. Chem., 2015, 35(1): 121-128.

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[1] (a) Amara, Z.; Caron, J.; Joseph, D. Nat. Prod. Rep. 2013, 30, 1211. (b) Lin, D.; Wang, J.; Liu, H. Chin. J. Org. Chem. 2013, 33, 2098 (in Chinese). (林岱宗, 王江, 柳红, 有机化学, 2013, 33, 2098.) (c) Weiner, B.; Szymański, W.; Janssen, D. B.; Minnaard, A. J.; Feringa, B. L. Chem. Soc. Rev. 2010, 39, 1656. (d) Mikami, K.; Fustero, S.; Sánchez-Roselló, M.; Aceña, J. L.; Soloshonok, V.; Sorochinsky, A. Synthesis 2011, 3045. (e) Cardillo, G.; Tomasini, C. Chem. Soc. Rev. 1996, 25, 117.
[2] For selected reviews on aza-Michael reaction, see: (a) Wang, J.; Li, P.; Choy, P. Y.; Chan, A. S. C.; Kwong, F. Y. ChemCatChem 2012, 4, 917. (b) Enders, D.; Wang, C.; Liebich, J. X. Chem. Eur. J. 2009, 15, 11058. (c) Xu, L.-W.; Xia, C.-G. Eur. J. Org. Chem. 2005, 633. (d) Xu, L.-W.; Xia, C.-G.; Wu, H.; Yang, L.; Zhou, W.; Zhang, Y. Chin. J. Org. Chem. 2005, 25, 167 (in Chinese). (徐利文, 夏春谷, 吴乎格吉乐土, 杨磊, 周伟, 张妍, 有机化学, 2005, 25, 167.)
[3] (a) Gandelman, M.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 2393. (b) Wang, J.; Li, H.; Zu, L.; Wang, W. Org. Lett. 2006, 8, 1391. (c) Dinér, P.; Nielsen, M.; Marigo, M.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2007, 46, 1983. (d) Uria, U.; Vicario, J. L.; Badía, D.; Carrillo, L. Chem. Commun. 2007, 2509. (e) Liu, B. K.; Wu, Q.; Qian, X. Q.; Lv, D. S.; Lin, X. F. Synthesis 2007, 2653. (f) Wang, J.; Zu, L.; Li, H.; Xie, H.; Wang, W. Synthesis 2007, 2576. (g) Lin, Q.; Meloni, D.; Pan, Y.; Xia, M.; Rodgers, J.; Shepard, S.; Li, M.; Galya, L.; Metcalf, B.; Yue, T.-Y.; Liu, P.; Zhou, J. Org. Lett. 2009, 11, 1999. (h) Luo, G. S.; Zhang, S. L.; Duan, W. H.; Wang, W. Synthesis 2009, 1564. (i) Lv, J.; Wu, H.; Wang, Y. Eur. J. Org. Chem. 2010, 2073. (j) Zhou, Y.; Li, X.; Li, W.; Wu, C.; Liang, X.; Ye, J. Synlett 2010, 2357. (k) Hou, X.; Hemit, H.; Yong, J.; Nie, L.; Aisa, H. A. Synth. Commun. 2010, 40, 973. (l) Guo, H.-M.; Yuan, T.-F.; Niu, H.-Y.; Liu, J.-Y.; Mao, R.-Z.; Li, D.-Y.; Qu, G.-R. Chem. Eur. J. 2011, 17, 4095. (m) Lee, S.-J.; Youn, S.-H.; Cho, C.-W. Org. Biomol. Chem. 2011, 9, 7734. (n) Li, H.; Zhao, J.; Zeng, L.; Hu, W. J. Org. Chem. 2011, 76, 8064. (o) Uria, U.; Reyes, E. m.; Vicario, J. L.; Badía, D.; Carrillo, L. Org. Lett2015-1-28. 2011, 13, 336. (p) Wang, J.; Wang, W.; Liu, X.; Hou, Z.; Lin, L.; Feng, X. Eur. J. Org. Chem. 2011, 2039. (q) Wu, H.; Tian, Z.; Zhang, L.; Huang, Y.; Wang, Y. Adv. Synth. Catal. 2012, 354, 2977.
[4] (a) Giornal, F.; Pazenok, S.; Rodefeld, L.; Lui, N.; Vors, J.-P.; Leroux, F. R. J. Fluorine Chem. 2013, 152, 2. (b) Lamberth, C. Heterocycles 2007, 71, 1467.
[5] Raju, H.; Chandrappa, S.; Prasanna, D. S.; Ananda, H.; Nagamani, T. S.; Byregowda, S. M.; Rangappa, K. S. Recent Pat. Anti-Cancer Drug Discovery 2011, 6, 186.
[6] Bekhit, A. A.; Hymete, A.; Bekhit, A. E. A.; Damtew, A.; Aboul-Enein, H. Y. Mini-Rev. Med. Chem. 2010, 10, 1014.
[7] Secci, D.; Bolasco, A.; Chimenti, P.; Carradori, S. Curr. Med. Chem. 2011, 18, 5114.
[8] Kumar, G. G.; Vikas, K.; Vinod, K. Res. J. Chem. Environ. 2011, 15, 90.
[9] Peng, X.-M.; Cai, G.-X.; Zhou, C.-H. Curr. Top. Med. Chem. 2013, 13, 1963.
[10] (a) Fustero, S.; Sánchez-Roselló, M.; Barrio, P.; Simón-Fuentes, A. Chem. Rev. 2011, 111, 6984. (b) Fustero, S.; Simón-Fuentes, A.; Sanz-Cervera, J. F. Org. Prep. Proced. Int. 2009, 41, 253.
[11] Qian, C.; Xu, J.-M.; Wu, Q.; Lv, D.-S.; Lin, X.-F. Tetrahedron Lett. 2007, 48, 6100.
[12] Xu, J.-M.; Qian, C.; Liu, B.-K.; Wu, Q.; Lin, X.-F. Tetrahedron 2007, 63, 986.
[13] Wang, J.; Li, P.-F.; Chan, S. H.; Chan, A. S. C.; Kwong, F. Y. Tetrahedron Lett. 2012, 53, 2887.
[14] Wu, Y.; Wang, J.; Li, P.; Kwong, F. Y. Synlett 2012, 788.
[15] (a) Kawatsura, M.; Aburatani, S.; Uenishi, J. Tetrahedron 2007, 63, 4172. (b) Aburatani, S.; Kawatsura, M.; Uenishi, J. Heterocycles 2007, 71, 189.
[16] Wu, Y.-J. Tetrahedron Lett. 2006, 47, 8459.
[17] Uddin, M. I.; Nakano, K.; Ichikawa, Y.; Kotsuki, H. Synlett 2008, 1402.
[18] Lee, I. Y. C.; Lee, K. C.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 3535.
[19] Bhanuchandra, M.; Kuram, M. R.; Sahoo, A. K. Org. Biomol. Chem. 2012, 10, 3538.
[20] During preparation of this manuscript, an organocatalytic asymmetric aza-Michael addition of pyrazole to chalcone was developed. See: Li, P.; Fang, F.; Chen, J.; Wang, J. Tetrahedron: Asymmetry 2014, 25, 98.
[21] (a) Lehmann, F. Synlett 2004, 2447. (b) Duan, X.-F.; Zhang, Z.-B. Chin. J. Org. Chem. 2006, 26, 573 (in Chinese). (段新方, 张站斌, 有机化学, 2006, 26, 573.)
[22] (a) Liu, D.; Gao, W.; Wang, C.; Zhang, X. Angew. Chem., Int. Ed. 2005, 44, 1687. (b) Calow, A. D. J.; Batsanov, A. S.; Fernández, E.; Solé, C.; Whiting, A. Chem. Commun. 2012, 48, 11401.

碳酸铯催化吡唑与α,β-不饱和酮的氮杂Michael反应

Cesium Carbonate Catalyzed Aza-Michael Addition of Pyrazole to α,β-Unsaturated Ketones

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