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Synlett 2003(1): 0097-0101
DOI: 10.1055/s-2003-36235
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Facile Method for the Construction of Highly Substituted Acetonitriles and Olefins. Malononitriles as Acetonitrile Carbanion and Alkylidene Dianion Equivalents

Ting-Yueh Tsaia,b, Kak-Shan Shiaa, Hsing-Jang Liu*a,b
a Department of Chemistry, National Tsing Hua University, Hsinchu, 30013, Taiwan, R.O.C.
b Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529, Taiwan, R.O.C.
Fax: +886(3)5720711; e-Mail: hjliu@mx.nthu.edu.tw;
Further Information

Publication History

Received 4 October 2002
Publication Date:
18 December 2002 (online)

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Abstract

The use of malononitrile to facilitate the preparation of highly substituted nitriles, via reductive alkylation/addition, and olefins, via a combination of reductive addition and reductive elimination, is described.

Key words

malononitrile - reduction - alkylation - addition - nitriles - olefination

    References

  • For leading references, see:
  • 1a Grashey R. In Comprehensive Organic Synthesis   Vol. 6:  Trost BM. Fleming I. Winterfeldt E. Pergamon Press; Oxford, UK: 1991.  Chap. 1.8. p.225-259  
    Google Scholar
  • 1b Larock RC. Comprehensive Organic Transformations   John Wiley and Sons, Inc.; New York: 1999. 
    Google Scholar
  • For leading references, see:
  • 2a Fleming I. Barbero A. Walter D. Chem. Rev.  1997,  97:  2063 
    CrossrefGoogle Scholar
  • 2b van Staden LF. Gravestock D. Ager D. Chem. Soc. Rev.  2002,  31:  195 
    CrossrefGoogle Scholar
  • 4 Julia M. Paris JM. Tetrahedron Lett.  1973,  4933 
    CrossrefGoogle Scholar
  • 5 Kocienski P. Chem. Ind. (London)  1981,  548 
    Google Scholar
  • 6 Oediger H. Moller F. Liebigs Ann. Chem.  1976,  348 
    Google Scholar
  • For another procedure, see:
  • 7a Diez-Barra E. de la Hoz A. Moreno A. Sanchez-Verdu P. J. Chem. Soc., Perkin Trans. 1  1991,  2589 
    CrossrefGoogle Scholar
  • 7b Diez-Barra E. de la Hoz A. Moreno A. Sanchez-Verdu P. J. Chem. Soc., Perkin Trans. 1  1991,  2593 
    CrossrefGoogle Scholar
  • 10 For the preparation of a stock solution of LN in THF, see: Liu HJ. Shang X. Tetrahedron Lett.  1998,  39:  367 
    CrossrefGoogle Scholar
  • 12a Marshall JA. Karas LJ. J. Am. Chem. Soc.  1978,  100:  3615 
    Google Scholar
  • 12b Marshall JA. Karas LJ. Royce RD. J. Org. Chem.  1979,  44:  2994 
    Google Scholar
  • 13 Pojer PM. Angyal S. Tetrahedron Lett.  1976,  3067 
    CrossrefGoogle Scholar
  • 14 Cohen T. Kreethadumrongdat T. Liu X. Kulkarni V. J. Am. Chem. Soc.  2001,  123:  3478 
    CrossrefGoogle Scholar
3

Many of the established olefination methods are not generally effective for the formation of highly substituted olefins. For example, Julia olefination, [4] which is an excellent process for the preparation of disubstituted alkenes and some trisubstituted ones, fails with most tetra-substituted alkenes. [5]

8

The Chemical Abstract Service registry numbers of known compounds are cited in Table [1] and Table [2] .

9

Satisfactory spectral and elemental or HRMS analytical data were obtained for all new compounds.

11

Spectral data for compound 5: IR(neat): 3435 (OH), 2239 (CN), 1603 (C=C) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.45 (d, J = 2.0 Hz, 1 H), 7.33-7.26 (m, 10 H), 6.43 (d, J = 3.2 Hz, 1 H), 6.40 (dd, J 1 = 3.2 Hz, J 2 = 2.0 Hz, 1 H), 4.75 (s, 1 H), 3.09 (d, J = 13.8 Hz, 1 H), 3.07 (d, J = 13.6 Hz, 1 H), 2.98 (d, J = 13.8 Hz, 1 H), 2.65 (d, J = 13.6 Hz, 1 H), 2.42 (br s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 151.7 (C), 142.6 (CH), 135.1 (C), 134.9 (C), 130.6 (CH), 130.4 (CH), 128.4 (2 CH), 127.2 (2 CH), 120.9 (C), 110.6 (CH), 109.4 (CH), 68.4 (CH), 49.1 (C), 38.2 (CH2), 37.7 (CH2). HRMS [M+]: 331.1412 (calcd for C21H19NO2: 317.1415).

15

Spectral data for compound 6: IR (neat): 2237 (CN), 1603 (C=C) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.48 (d, J = 1.8 Hz, 1 H), 7.33-7.26 (m, 10 H), 4.13 (s, 1 H), 3.22 (s, 3 H), 3.12 (d, J = 13.8 Hz, 1 H), 3.07 (d, J = 13.4 Hz, 1 H), 3.04 (d, J = 13.8 Hz, 1 H), 2.68 (d, J = 13.4 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 149.5 (C), 143.1 (CH), 135.2 (C), 135.1 (C), 130.6 (CH), 130.3 (CH), 128.3 (CH), 128.2 (CH), 127.2 (CH), 127.1 (CH), 120.8 (C), 111.3 (CH), 110.3 (CH), 76.6 (CH), 56.7 (CH3), 48.7 (C), 38.6 (CH2), 37.9 (CH2); HRMS [M+]: 331.1575 (calcd for C22H21NO2: 331.1572).

16

Spectral data for compound 7: IR (neat): 1600 (C=C) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.34 (d, J = 1.8 Hz, 1 H), 7.30-7.14 (m, 10 H), 6.35 (dd, J 1 = 1.8 Hz, J 2 = 3.2 Hz, 1 H), 6.24 (d, J = 3.2 Hz, 1 H), 6.22 (s, 1 H), 3.76 (s, 2 H), 3.36 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 152.8 (C), 141.1 (CH), 139.7 (C), 139.3 (C), 139.2 (C), 129.2 (CH), 128.7 (CH), 128.4 (CH), 128.3 (CH), 126.2 (CH), 126.1 (CH), 117.1 (CH), 111.0 (CH), 108.4 (CH), 43.5 (CH2), 37.0 (CH2); HRMS [M+]: 274.1357 (calcd for C20 H18: 274.1351).