Citation: SUN Xiang-Ting, ZHANG Dong-Ju, FENG Da-Cheng, LIU Cheng-Bu. Asymmetric Michael Addition between Nitroolefins and Sulfur Ylides Catalyzed by a Thiourea Organocatalyst[J]. Acta Physico-Chimica Sinica, ;2012, 28(03): 561-566. doi: 10.3866/PKU.WHXB201201112 shu

Asymmetric Michael Addition between Nitroolefins and Sulfur Ylides Catalyzed by a Thiourea Organocatalyst

1.
School of Chemistry and Chemical Engineering, Institute of Theoretical Chemistry, Shandong University, Jinan 250100, P. R. China

Received Date: 5 December 2011
Available Online: 11 January 2012
Fund Project: 国家自然科学基金(20873076) (20873076)教育部博士点基金(200804220009)资助项目 (200804220009)

Using density functional theory calculations, we have studied the 1-(2-chlorophenyl)-2-thiourea catalyzed reaction of nitrostyrene with a typical sulfur ylide to understand the Michael addition mechanism. Transition state structures for the C―C bond-forming step controlling the stereoselectivity of the reaction have been identified and their relative stabilities evaluated. The role of the catalyst in the reaction has also been determined. The calculated results show that the formation of the anti-product is energetically more favorable than that of the syn-product. Furthermore, the catalyst (proton donor) promotes the reaction by forming a double hydrogen-bonded complex with nitrostyrene (proton acceptor), where the charge transfer between the donor and acceptor increases the eletrophilicity of β-C atom of the nitrostyrene, favoring the nucleophilic attack of the sulfur ylide.
- Thiourea,
- Nitroolefin,
- Sulfur ylide,
- Asymmetric Michael addition,
- Density functional theory
1. [1]
  (1) Brown, S. P.; odwin, N. C.; MacMillan, D.W. C. J. Am. Chem. Soc. 2003, 125, 1192.
2. [2]
  (2) Enders, D.; Seki, A. Synlett. 2002, 26.
3. [3]
  (3) Andrey, O.; Alexakis, A; Bernardinelli, G. Org Lett. 2003, 5, 2559.
4. [4]
  (4) Ishii, T.; Fujioka, S.; Sekiguchi, Y.; Kotsuki, H. J. Am. Chem. Soc. 2004, 126, 9558.
5. [5]
  (5) List, B.; Prjarliev, P.; Martin, H. J. Org. Lett. 2001, 3, 2423.
6. [6]
  (6) Okino, T.; Hoashi, Y.; Furukawa, T.; Takemoto, Y. J. Am. Chem. Soc. 2005, 127, 119.
7. [7]
  (7) Alexakis, A.; Andrey, O. Org. Lett. 2002, 4, 3611.
8. [8]
  (8) Betancort, J. M.; Barbas, C. F. Org. Lett. 2001, 3, 3737.
9. [9]
  (9) Lu, L. Q.; Cao, Y. J.; Liu, X. P.; An, J.; Yao, C. J.; Ming, Z. H.; Xiao,W. J. J. Am. Chem. Soc. 2008, 130, 6946.
10. [10]
  (10) Hay, P. J.;Wadt,W. R. J. Chem. Phys. 1985, 82, 299.
11. [11]
  (11) Hay, P. J.;Wadt,W. R. J. Chem. Phys. 1985, 82, 270.
12. [12]
  (12) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al . Gaussian 03, Revision D.01; Gaussian Inc.:Wallingford, CT, 2004.
13. [13]
  (13) Fu, A. P.; Li, H. L.; Yuan, S. P.; Si, H. Z.; Duan, Y. B. J. Org. Chem. 2008, 73, 5264.
14. [14]
  (14) Fu, A. P.; Li, H. L.; Tian, F. H.; Yuan, S. P.; Si, H. Z.; Duan, Y. B. Tetrahedron: Asymmetry 2008, 19, 1288
15. [15]
  (15) Zheng,W. R.; Xu, L. J.; Huang, T.; Yang, Q.; Chen, Z. C. Res. Chem. Intermed. 2011, 37, 31.
16. [16]
  (16) Zheng,W. R.; Fu, Y.; Shen, K.; Liu, L.; Guo, Q. X. J. Mol. Struct: Theochem 2007, 822, 103.
17. [17]
  (17) Zheng,W. R.; Fu, Y.; Liu, L.; Guo, Q. X. Acta Physico-Chimica Sinica 2007, 23, 1018. [郑文锐, 傅尧, 刘磊, 郭庆祥. 物理化学学报, 2007, 23, 1018.]
18. [18]
  (18) Hoashi, Y.; Okino, T.; Takemoto, Y. Angew. Chem. Int. Edit. 2005, 44, 4032.
19. [19]
  (19) Xu, X.; Yabuta, T.; Yuan, P.; Takemoto, Y. Synlett 2006, 136.
20. [20]
  (20) Xu, X.; Furukawa, T.; Okino, T.; Miyabe, H.; Takemoto, Y. Chem. Eur. J. 2006, 12, 466.
21. [21]
  (21) Li, Q.; Huang, F. Q. Acta Physico-Chimica Sinica 2005, 21, 52. [李权, 黄方千. 物理化学学报, 2005, 21, 52.]
22. [22]
  (22) Tan, B.; Zeng, X. F.; Lu, Y. P.; Chua, P. J.; Zhong, G. F. Org. Lett. 2009, 11, 1927.
23. [23]
  (23) Lu, N.; Meng, L.; Chen, D. Z.; Zhang, G. Q. J. Phys. Chem. A. Articles ASAP.
24. [24]
  (24) Yang, H.;Wong, M.W. J. Org. Chem. 2011, 76, 7399.
25. [25]
  (25) Marju, L.; Kerti, A.; Merle, U.; Toomas, T.; Tonis, K.; Margus, L. J. Org. Chem. 2009, 74, 3722.
1. [1]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
3. [3]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
4. [4]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
5. [5]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
6. [6]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
7. [7]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
8. [8]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
9. [9]
  Lihui Jiang , Wanrong Dong , Hua Yang , Yongqing Xia , Hongjian Peng , Jun Yuan , Xiaoqian Hu , Zihan Zeng , Yingping Zou , Yiming Luo . Study on Extraction of p-Hydroxyacetophenone. University Chemistry, 2024, 39(11): 259-268. doi: 10.12461/PKU.DXHX202402056
10. [10]
  Hua Hou , Baoshan Wang . Course Ideology and Politics Education in Theoretical and Computational Chemistry. University Chemistry, 2024, 39(2): 307-313. doi: 10.3866/PKU.DXHX202309045
11. [11]
  Yanhui XUE , Shaofei CHAO , Man XU , Qiong WU , Fufa WU , Sufyan Javed Muhammad . Construction of high energy density hexagonal hole MXene aqueous supercapacitor by vacancy defect control strategy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1640-1652. doi: 10.11862/CJIC.20240183
12. [12]
  Qiqi Li , Su Zhang , Yuting Jiang , Linna Zhu , Nannan Guo , Jing Zhang , Yutong Li , Tong Wei , Zhuangjun Fan . 前驱体机械压实制备高密度活性炭及其致密电容储能性能. Acta Physico-Chimica Sinica, 2025, 41(3): 2406009-. doi: 10.3866/PKU.WHXB202406009
13. [13]
  Jia Yao , Xiaogang Peng . Theory of Macroscopic Molecular Systems: Theoretical Framework of the Physical Chemistry Course in the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 27-37. doi: 10.12461/PKU.DXHX202408117
14. [14]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
15. [15]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
16. [16]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
17. [17]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
18. [18]
  Keweiyang Zhang , Zihan Fan , Liyuan Xiao , Haitao Long , Jing Jing . Unveiling Crystal Field Theory: Preparation, Characterization, and Performance Assessment of Nickel Macrocyclic Complexes. University Chemistry, 2024, 39(5): 163-171. doi: 10.3866/PKU.DXHX202310084
19. [19]
  Qiang Xu , Rong Zhang , Liyan Zhang , Jinxuan Liu , Shuo Wu , Rongwen Lv . Exploration and Practice of Ideological and Political Education Construction in the Course of Practical Instrument Analysis Theory. University Chemistry, 2024, 39(6): 132-136. doi: 10.3866/PKU.DXHX202311018
20. [20]
  Yaling Chen . Basic Theory and Competitive Exam Analysis of Dynamic Isotope Effect. University Chemistry, 2024, 39(8): 403-410. doi: 10.3866/PKU.DXHX202311093

Get Citation

PDF

XML

Metrics

PDF Downloads(915)
Abstract views(3173)
HTML views(115)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142