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

  • 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.
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    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.

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