Download PDF
Synlett 2012(5): 788-790  
DOI: 10.1055/s-0031-1290359
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Catalyst-Free Efficient Aza-Michael Addition of Azoles to Nitroalkenes

Yinuo Wua, Jun Wangb, Pengfei Li*a,c, Fuk Yee Kwong*a
a State Key Laboratory for Chirosciences and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong, P. R. of China
Fax: +852(2364)9932; e-Mail: flyli1980@yahoo.com.cn; e-Mail: bcfyk@inet.polyu.edu.hk;
b School of Chinese Medicine, Hong Kong Baptist University, Hong Kong, P. R. of China
c Institute of Creativity, Faculty of Science, Hong Kong Baptist University, Hong Kong, P. R. of China
Further Information

Publication History

Received 19 December 2011
Publication Date:
24 February 2012 (online)

    Permissions and Reprints All articles of this category

Abstract

An efficient aza-Michael addition of azole to nitroalkene has been developed. In this conjugate addition, no catalyst was employed and azole reacted with nitroolefin smoothly to afford new C-N bond adducts in good to excellent yields.

Key words

Michael addition - azole - nitroolefin - nitroalkene - amination

    References and Notes

  • For some selected references, see:
  • 1a Cardillo G. Tomasini C. Chem. Soc. Rev.  1996,  25:  117 
    Google Scholar
  • 1b Davies SG. Smith AD. Price PD. Tetrahedron: Asymmetry  2005,  16:  2833 
    Google Scholar
  • 1c Chandrasekhar S. Reddy NR. Rao YS. Tetrahedron  2006,  62:  12098 
    Google Scholar
  • 1d Dorbec M. Florent JC. Monneret C. Rager MN. Bertounesque E. Tetrahedron  2006,  62:  11766 
    Google Scholar
  • 1e Prakech M. Srivastava S. Leek DM. Arya P. J. Comb. Chem.  2006,  8:  762 
    Google Scholar
  • 1f Dorbec M. Florent JC. Monneret C. Rager MN. Bertounesque E. Synlett  2006,  591 
    Google Scholar
  • 1g Ihara M. Chem. Pharm. Bull.  2006,  54:  765 
    Google Scholar
  • For reviews on enantioselective aza-Michael addition, see:
  • 2a Vicario JL. Badía L. Carrillo L. Etxebarria J. Reyes E. Ruiz N. Org. Prep. Proced. Int.  2005,  37:  513 
    Google Scholar
  • 2b Xu LW. Xia CG. Eur. J. Org. Chem.  2005,  633 
    Google Scholar
  • 2c Vicario JL. Badía D. Carrillo L. Synthesis  2007,  2065 
    Google Scholar
  • 2d Enders D. Wang C. Liebich JX. Chem. Eur. J.  2009,  15:  11058 
    Google Scholar
  • 2e Krishna PR. Sreeshailam A. Srinivas R. Tetrahedron  2009,  65:  9657 
    Google Scholar
  • For references on catalytic non-enantioselective aza-Michael addition, see:
  • 3a Xu LW. Li L. Xia CG. Zhou SL. Li JW. Hu XX. Synlett  2003,  2337 
    Google Scholar
  • 3b Xu LW. Xia CG. Tetrahedron Lett.  2004,  45:  4507 
    Google Scholar
  • 3c Chaudhuri MK. Hussain S. Kantam ML. Neelima B. Tetrahedron Lett.  2005,  46:  8329 
    Google Scholar
  • 3d Firouzabadi H. Iranpoor N. Jafari AA. Adv. Synth. Catal.  2005,  347:  655 
    Google Scholar
  • 3e Khalafi-Nezhad A. Zarea A. Rad MNS. Mokhtari B. Parhami A. Synthesis  2005,  419 
    Google Scholar
  • 3f Yang L. Xu LW. Zhou W. Li L. Xia CG. Tetrahedron Lett.  2006,  47:  7723 
    Google Scholar
  • 3g Han X. Tetrahedron Lett.  2007,  48:  2845 
    Google Scholar
  • 3h Kawatsura M. Aburatani S. Uenishi J. Tetrahedron  2007,  63:  4172 
    Google Scholar
  • 4a Dinér P. Nielsen M. Marigo M. Jørgensen KA. Angew. Chem. Int. Ed.  2007,  46:  1983 
    Google Scholar
  • 4b Wang J. Li H. Zu L. Wang W. Org. Lett.  2006,  8:  1391 
    Google Scholar
  • 4c Wang J. Zu L. Li H. Xie H. Wang W. Synthesis  2007,  2576 
    Google Scholar
  • 4d Uria U. Vicario JL. Badia D. Carrillo L. Chem. Commun.  2007,  2509 
    Google Scholar
  • 4e Luo G. Zhang S. Duan W. Wang W. Synthesis  2009,  1564 
    Google Scholar
  • 4f Gogoi S. Zhao C.-G. Ding D. Org. Lett.  2009,  11:  2249 
    Google Scholar
  • 4g Zhou Y. Li X. Li W. Wu C. Liang X. Ye J. Synlett  2010,  2357 
    Google Scholar
  • 5 Zaderenko P. López MC. Ballesteros P. J. Org. Chem.  1996,  61:  6825 
    Google Scholar
  • 6 Uddin MI. Nakano K. Ichikawa Y. Kotsuki H. Synlett  2008,  1402 
    Google Scholar
  • 7 Moran J. Dornan P. Beauchemin AM. Org. Lett.  2007,  9:  3893 
    Google Scholar
  • 8 Wu Y.-J. Tetrahedron Lett.  2006,  47:  8459 
    Google Scholar
  • For reviews see:
  • 9a Berner OM. Tedeschi L. Enders D. Eur. J. Org. Chem.  2002,  1877 
    Google Scholar
  • 9b Sulzer-Mossé S. Alexakis A. Chem. Commun.  2007,  3123 
    Google Scholar
  • 10a Nef JU. Justus Liebigs Ann. Chem.  1894,  280:  263 
    Google Scholar
  • 10b Pinnick HW. Org. React. (N. Y.)  1990,  38:  655 
    Google Scholar
  • 11 Tamura R. Kamimura A. Ono N. Synthesis  1991,  423 
    Google Scholar
  • For some selected references, see:
  • 12a Loyd DH. Nichols DE. J. Org. Chem.  1986,  51:  4294 
    Google Scholar
  • 12b Barrett AGM. Spilling CD. Tetrahedron Lett.  1988,  29:  5733 
    Google Scholar
  • 12c Beck AK. Seebach D. Chem. Ber.  1991,  124:  2897 
    Google Scholar
  • 12d Maeri RE. Heinzer J. Seebach D. Liebigs Ann.  1995,  1193 
    Google Scholar
  • 12e Poupart MA. Fazal G. Goulet S. Mar LT. J. Org. Chem.  1999,  64:  1356 
    Google Scholar
  • 13a Meyer V. Wurster C. Ber. Dtsch. Chem. Ges.  1873,  6:  1168 
    Google Scholar
  • 13b Kamlet ML. Kaplan LA. Dacons JC. J. Org. Chem.  1961,  26:  4371 
    Google Scholar
  • 14 Mukayama T. Hoshino T. J. Am. Chem. Soc.  1960,  82:  5339 
    Google Scholar
  • 15 Nielsen M. Zhuang W. Jørgensen KA. Tetrahedron  2007,  63:  5849 
    Google Scholar
  • For our previous interest in the reaction of β,γ-unsaturated α-keto ester moiety, see:
  • 16a Li P. Zhao J. Li F. Chan ASC. Kwong FY. Org. Lett.  2010,  12:  5616 
    Google Scholar
  • 16b Li P. Chan SH. Chan ASC. Kwong FY. Adv. Synth. Catal.  2011,  353:  1179 
    Google Scholar
  • 16c Li P. Chan SH. Chan ASC. Kwong FY. Org. Biomol. Chem.  2011,  9:  7997 
    Google Scholar
17

¹H NMR data of adduct: ¹H NMR (400 MHz, CDCl3): δ = 7.59 (s, 1 H), 7.43 (d, J = 2.0 Hz, 1 H), 7.36-7.38 (m, 3 H), 7.28-7.30 (m, 2 H), 6.29 (t, J = 1.8 Hz, 1 H), 6.12 (dd, J = 4.8, 9.6 Hz, 1 H), 5.63 (dd, J = 9.6, 14.0 Hz, 1 H), 4.87 (dd, J = 4.8, 14.0 Hz, 1 H).

18

¹H NMR data of adduct: ¹H NMR (400 MHz, CDCl3): δ = 7.29-7.36 (m, 3 H), 7.22-7.24 (m, 2 H), 5.96 (dd, J = 4.4, 10.0 Hz, 1 H), 5.83 (s, 1 H), 5.67 (dd, J = 9.8, 14.2 Hz, 1 H), 4.81 (dd, J = 4.4, 14.0 Hz, 1 H), 2.23 (m, 3 H), 2.18 (m, 3 H).

19

¹H NMR data of adduct: ¹H NMR (400 MHz, CDCl3): δ = 7.28-7.39 (m, 5 H), 7.05-7.12 (m, 2 H), 6.67-6.71 (m, 2 H), 5.63 (dd, J = 6.8, 8.4 Hz, 1 H), 5.03 (dd, J = 8.8, 12.0 Hz, 1 H), 4.92 (dd, J = 10.6, 12.2 Hz, 1 H), 3.42-3.48 (m, 1 H), 3.13-3.20 (m, 1 H), 2.86-3.01 (m, 2 H).

20

Unless noted otherwise, the reaction was carried out as following: to a solution of CH2Cl2 (0.1 mL) were added nitroalkene 1 (0.1 mmol) and azole 2 (0.13 mmol). The reaction mixture was stirred at r.t. for 24 h and then the solvent was removed under vacuum. The residue was purified by column chromatography on silica gel to yield the desired Michael adducts 3.