RSS-Feed abonnieren
PDF herunterladen
DOI: 10.1055/s-2003-36235
A Facile Method for the Construction of Highly Substituted Acetonitriles and Olefins. Malononitriles as Acetonitrile Carbanion and Alkylidene Dianion Equivalents
Publikationsverlauf
Publikationsdatum:
18. Dezember 2002 (online)
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
- 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.225-259MissingFormLabel - 1b
Larock RC. Comprehensive Organic Transformations John Wiley and Sons, Inc.; New York: 1999.MissingFormLabel - For leading references, see:
- 2a
Fleming I.Barbero A.Walter D. Chem. Rev. 1997, 97: 2063 - 2b
van Staden LF.Gravestock D.Ager D. Chem. Soc. Rev. 2002, 31: 195 - 4
Julia M.Paris JM. Tetrahedron Lett. 1973, 4933 - 5
Kocienski P. Chem. Ind. (London) 1981, 548 - 6
Oediger H.Moller F. Liebigs Ann. Chem. 1976, 348 - 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 - 7b
Diez-Barra E.de la Hoz A.Moreno A.Sanchez-Verdu P. J. Chem. Soc., Perkin Trans. 1 1991, 2593 - 10 For the preparation of a stock solution
of LN in THF, see:
Liu HJ.Shang X. Tetrahedron Lett. 1998, 39: 367 - 12a
Marshall JA.Karas LJ. J. Am. Chem. Soc. 1978, 100: 3615 - 12b
Marshall JA.Karas LJ.Royce RD. J. Org. Chem. 1979, 44: 2994 - 13
Pojer PM.Angyal S. Tetrahedron Lett. 1976, 3067 - 14
Cohen T.Kreethadumrongdat T.Liu X.Kulkarni V. J. Am. Chem. Soc. 2001, 123: 3478
References
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]
8The Chemical Abstract Service registry numbers of known compounds are cited in Table [1] and Table [2] .
9Satisfactory spectral and elemental or HRMS analytical data were obtained for all new compounds.
11Spectral 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).
15Spectral 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).
16Spectral 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).