Citation: Bai Bing, Wang Long, Yang Jing, Cai Lili, Liu Qianjin, Xi Gaolei, Zhao Zhiwei, Mao Duobin, Chen Zhifei. Asymmetric Conjugate Addition of 1, 3-Diketone to Nitroalkenes Catalyzed by Bifunctional Thiourea-Amide Organocatalysts[J]. Chinese Journal of Organic Chemistry, ;2019, 39(4): 1053-1063. doi: 10.6023/cjoc201809015 shu

Asymmetric Conjugate Addition of 1, 3-Diketone to Nitroalkenes Catalyzed by Bifunctional Thiourea-Amide Organocatalysts

Bai Bing ^a ,
Wang Long ^a ,
Yang Jing ^a ,
Cai Lili ^b ,
Liu Qianjin ^b ,
Xi Gaolei ^b ,
Zhao Zhiwei ^b ,
Mao Duobin ^a,, ,
Chen Zhifei ^b,,

a.
School of Food & Biological Engineering, Zhengzhou University of Light Industry, Zhengzhou 450000
b.
Technology Center, China Tobacco Henan Industrial Co., Ltd., Zhengzhou 450000

Corresponding author: Mao Duobin, maoduobin@sohu.com Chen Zhifei, chenzhifei@126.com
Received Date: 10 September 2018
Revised Date: 14 November 2018
Available Online: 28 April 2018
Fund Project: the Department of Science and Technology of Henan Province 172102210068Project supported by the Department of Science and Technology of Henan Province (No. 172102210068) and the Zhengzhou University of Light Industry (No. 2013BSJJ009)the Zhengzhou University of Light Industry 2013BSJJ009

Figures(5)

New bifunctional chiral thiourea-amide organocatalysts were developed. Their applications in asymmetric conjugate addition of 2, 4-pentandione to various nitroalkenes were investigated. The corresponding adducts were obtained in excellent yields with high enantioselectivities up to 94% ee in present of 1 mol% catalyst. The catalytic system could also suit for various nitroalkenes bearing electron-donating or electron-withdrawing groups. The preliminary structure-activity relationship study reveals that the acyl group in pyrrolidine N position plays an important role in catalyzing the reaction.
- thiourea-amide,
- organocatalyst,
- Michael addition,
- asymmetric
1. [1]
  (a) Okino, T.; Hoashi, Y.; Furukawa, T.; Xu, X.; Takemoto, Y. J. Am. Chem. Soc. 2005, 127, 119.
  (b) Bhattarai, B.; Nagorny, P. Org. Lett. 2018, 20, 154.
  (c) Hirama, T.; Umemura, T. Kogure, N.; Kitajima, M.; Takayama, H. Tetrahedron Lett. 2017, 58, 223.
  (d) Amara, Z.; Caron, J.; Joseph, D. Nat. Prod. Rep. 2013, 30, 1211.
2. [2]
  (a) Terada, M.; Ube, H.; Yaguchi, Y. J. Am. Chem. Soc. 2006, 128, 1451.
  (b) Yu, Lu.; Li, P. F. Tetrahedron Lett. 2014, 55, 3697.
  (c) Siew, W. E.; Ates, C.; Merschaerta, A.; Livingston, A. Green Chem. 2013, 15, 663.
  (d) Azad, C. S.; Khan, I. A.; Narula, A. K. Org. Biomol. Chem. 2016, 14, 11454.
3. [3]
  (a) Almaşi, D.; Alonso, D. A.; Gómez-Bengoa, E.; Nájera, C. J. Org. Chem. 2009, 74, 6163.
  (b) Servín, F. A.; Madrigal, D.; Romero, J. A.; Chávez, D.; Aguirre, G.; de Parrodi, C. A.; Somanathan, R. Tetrahedron Lett. 2015, 56, 2355.
  (c) Lu, Y. P.; Zou, G.; Zhao, G. Tetrahedron 2015, 71, 4137.
4. [4]
  (a) Andrés, J. M.; Manzano, R.; Pedrosa, R. Chem. Eur. J. 2008, 14, 5116.
  (b) Andrés, J. M.; González, M.; Maestro, A.; Naharro, D.; Pedrosa, R. Eur. J. Org. Chem. 2017, 2683.
  (c) Wang, C. J.; Zhang, Z. H.; Dong, X. Q.; Wu, X. J. Chem. Commun. 2008, 39, 1431.
5. [5]
  (a) Hirashima, S. I.; Nakashima, K.; Fujino, Y.; Arai, R.; Sakai, T.; Kawada, M.; Koseki, Y.; Murahashi, M.; Tada, N.; Itoh, A.; Miura T. Tetrahedron Lett. 2014, 55, 4619.
  (b) Li, H.; Zhang, X.; Shi, X.; Ji, N.; He, W.; Zhang, S. Y.; Zhang B. L. Adv. Synth. Catal. 2012, 354, 2264.
6. [6]
  (a) Andrés, J. M.; Losada, J.; Maestro, A.; Rodríguez-ferrer, P.; Pedrosa, R. J. Org. Chem. 2017, 82, 8444.
  (b) Tukhvatshin, R. S.; Kucherenko, A. S.; Nelyubina, Y. V.; Zlotin, S. G. ACS Catal. 2017, 7, 2981.
  (c) Işık, M.; Unver, M. Y.; Tanyeli, C. J. Org. Chem. 2015, 80, 828.
  (d) Kasaplar, P.; Riente, P.; Hartmann, C.; Pericàs, M. A. Adv. Synth. Catal. 2012, 354, 2905.
  (e) Malerich, J. P.; Hagihara, K.; Rawal, V. H. J. Am. Chem. Soc. 2008, 130, 14416.
7. [7]
  Xu, K.; Zhang, S.; Hu, Y. B.; Zha, Z. G.; Wang, Z. Y. Chem.-Eur. J. 2013, 19, 3573. doi: 10.1002/chem.v19.11
8. [8]
  Cao, C. L.; Ye, M. C.; Sun, X. L.; Tang, Y. Org. Lett. 2006, 8, 2901. doi: 10.1021/ol060481c
9. [9]
  (a) Wang, Z. Y.; Ban, S. R.; Yang, M. C.; Li, Q. S. Chirality 2016, 28, 721.
  (b) Cao, Y. J.; Lai, Y. Y.; Wang, X.; Lia, Y. J.; Xiao, W. J. Tetrahedron Lett. 2007, 48, 21.
  (c) Shen, Z. X.; Zhang, Y. Q.; Jiao, C. J.; Li, B.; Ding, J.; Zhang, Y. W. Chirality 2007, 19, 307.
  (d) Ban, S. R.; Zhu. X. X.; Zhang, Z. P.; Xie, H. Y.; Li, Q. S. Eur. J. Org. Chem. 2013, 2977.
10. [10]
  Vinayagam, P.; Vishwanath, M.; Kesavan, V. Tetrahedron: Asymmetry. 2014, 25, 568. doi: 10.1016/j.tetasy.2014.02.011
11. [11]
  Wommack, A. J.; Kingsbury, J. S. J. Org. Chem. 2013, 78, 10573. doi: 10.1021/jo401377a
12. [12]
  (a) Fu, J. Y.; Huang, Q. C.; Wang, Q. W.; Wang, L. X.; Xu, X Y. Tetrahedron Lett. 2010, 51, 4870.
  (b) Mei, K.; Zhang, S. L; He, S. T; Li, P.; Jin, M.; Xue, F.; Luo, G. S; Zhang, H. Y; Song. L. R; Duan, W. H; Wang, W. Tetrahedron Lett. 2008, 49, 2681.
  (c) Bai, J. F.; Xu, X. Y.; Huang, Q. C.; Peng, L.; Wang, L. X. Tetrahedron Lett. 2010, 51, 2803.
13. [13]
  (a) Wang, J.; Li, Hao.; Duan, W. H.; Zu, L. S.; Wang, W. Org. Lett. 2005, 7, 4713.
  (b) Weiner, B.; Szymanski, W.; Janssen, D. B.; Minnaard, A. J.; Feringa, B. L. Chem. Soc. Rev. 2010, 39, 1656.
  (c) Peddie, V.; Pietsch, M.; Bromfield, K. M.; Pike, R. N.; Duggan, P. J.; Abell, A. D. Synthesis 2010, 1845.
  (d) Bae, H. Y.; Song, C. E. ACS Catal. 2015, 5, 3613.
  (e) Liu, B.; Han, X.; Dong, Z.; Lv, H.; Zhou, H. B.; Dong, C. Tetrahedron: Asymmetry. 2013, 24, 1276.
14. [14]
  (a) Puglisi, A.; Benaglia, M.; Annunziata, R.; Rossi, D. Tetrahedron: Asymmetry. 2008, 19, 2258.
  (b) Peng, F. Z.; Shao, Z. H.; Fan, B. M.; Song, H.; Li G. P.; Zhang, H. B. J. Org. Chem. 2008, 73, 5202.
  (c) Lai, Q.; Li, Y.; Gong, Z. Y.; Liu, Q. W.; Wei, C. Y.; Song, Z. G. Chirality 2015, 27, 979.
15. [15]
  Dudziński, K.; Pakulska, A. M.; Kwiatkowski, P. Org. Lett. 2012, 14, 4222. doi: 10.1021/ol3019055
16. [16]
  Thai, K.; Wang, L.; Dudding, T.; Bilodeau, F.; Gravel, M. Org. Lett. 2010, 12, 5708. doi: 10.1021/ol102536s
17. [17]
  Minato, D.; Arimoto, H.; Nagasue, Y.; Demizu, Y.; Onomura, O. Tetrahedron 2008, 64, 6675. doi: 10.1016/j.tet.2008.05.015
18. [18]
  Flock, A. M.; Krebs, A.; Bolm, C. Synlett 2010, 1219.
19. [19]
  Ričko, S.; Svete, J.; Štefane, B.; Perdih, A.; Golobič, A.; Meden, A.; Grošelj, U. Adv. Synth. Catal. 2016, 358, 3786. doi: 10.1002/adsc.201600498
20. [20]
  Vural, U.; Durmaz, M.; Sirit, A. Org. Chem. Front. 2016, 3, 730. doi: 10.1039/C6QO00135A
21. [21]
  Gao, P.; Wang, C.; Wu, Y.; Zhou, Z.; Tang, C. Eur. J. Org. Chem. 2008, 4563.
22. [22]
  Jiang, X. X.; Zhang, Y. F.; Liu, X.; Zhang, G.; Lai, L. H.; Wu, L. P.; Zhang, J. N.; Wang, R. J. Org. Chem. 2009, 74, 5562. doi: 10.1021/jo9009276
23. [23]
  Ashokkumar, V.; Siva, A. Org. Biomol. Chem. 2015, 13, 10216. doi: 10.1039/C5OB01351H
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