123
L. MHAMDI ET AL.
4. Conclusions
The anionic activation in Henry and Darzens reactions
has been achieved by the addition of quaternary ammo-
nium salts leading to an exaltation of the reactivity of the
generated anions. The addition of a phase transfer cata-
lyst in the reaction medium leads to an increase in the
yield for the Henry reaction involving nitromethane and
various ketones as well as a remarkable reactivity in the
Darzens reaction. On the contrary, there is no reaction
with a α-chloroacetate acid whatever the medium, even
under PTC conditions.
5. References
[1] J. Franzen, J. Lofstedt, J. Falk and J. E. Backvall,
“Stereoselective Palladium-Catalyzed Carbocyclization of
Allenic Allylic Carboxylates,” Journal of American Che-
mical Society, Vol. 125, No. 46, 2003, pp. 14140-14148.
doi:10.1021/ja037398u
[2] S. M. Ma, S. C. Yu and S. H. Yin, “Studies on K2CO3-
Catalyzed 1,4-Addition of 1,2-Allenic Ketones with Di-
ethyl Malonate: Controlled Selective Synthesis of β,γ-
Unsaturated Enones and α-Pyrones,” The Journal of Or-
ganic Chemistry, Vol. 68, No. 23, 2003, pp. 8996-9002.
doi:10.1021/jo034633i
[3] C. A. Lin and F. T. Luo, “Polystyrene-Supported Recy-
clable Palladacycle Catalyst for Heck, Suzuki and Sono-
gashira Reactions,” Tetrahedron Letters, Vol. 44, No. 41,
2003, pp. 7565-7568. doi:10.1016/j.tetlet.2003.08.069
[4] D. O. Jang and D. H. Cho, “N-Ethylpiperidine Hypo-
phosphite Mediated Intermolecular Radical Carbon-
Carbon Bond Forming Reaction in Water,” Synlett, Vol. 9,
2002, pp. 1523-1525.
[5] B. E. Maryanoff and A. B. Reitz, “The Wittig Olefination
Reaction and Modifications Involving Phosphoryl-Sta-
bilized Carbanions. Stereochemistry, Mechanism, and Se-
lected Synthetic Aspects,” Chemical Reviews, Vol. 89,
No. 4, 1989, pp. 863-927. doi:10.1021/cr00094a007
[6] G. Rosini, R. Ballini, M. Petrini, E. Marotta and P. Righi,
“Recent Progress in the Synthesis and Reactivity of Ni-
troketones,” Organic Preparations and Procedures In-
ternational, Vol. 22, No. 6, 1990, pp. 707-746.
doi:10.1080/00304949009457902
[7] F. A. Luzzio, “The Henry Reaction: Recent Examples,”
Tetrahedron, Vol. 57, 2001, pp. 915-945.
[8] G. Klein, S. Pandiaraju and O. Reiser, “Activation of
Nitroaldol Reactions by Diethylzinc and Amino Alcohols
or Diamines as Promoters,” Tetrahedron Letters, Vol. 43,
No. 42, 2002, pp. 7503-7506.
doi:10.1016/S0040-4039(02)01768-9
[9] T. Jiang, H. Gao, B. Han, G. Zhao, Y. Chang, W. Wu, L.
Gao and G. Yang, “Ionic Liquid Catalyzed Henry Reac-
tions,” Tetrahedron Letters, Vol. 45, No. 12, 2004, pp.
2699-2701. doi:10.1016/j.tetlet.2004.01.129
[10] V. K. Aggarwal, G. Hynd, W. Picoul and J. L. Vasse,
“Highly Enantioselective Darzens Reaction of a Cam-
phor-Derived Sulfonium Amide to Give Glycidic Amides
and Their Applications in Synthesis,” Journal of Ameri-
can Chemical Society, Vol. 124, No. 34, 2002, pp. 9964-
9965. doi:10.1021/ja0272540
[11] N. E. Maguire, A. B. McLaren and J. B. Sweeney,
“Asymmetric Synthesis of Arylalanines via Asymmetric
aza-Darzens (ADZ) Reaction,” Synlett, Vol. 12, 2003, pp.
1898- 1900.
[12] Z. Wang, L. Xu, Z. Mu, C. Xia and H. Wang, “Efficient
Darzens Condensation Reactions of Aromatic Aldehydes
Catalyzed by Polystyrene-Supported Phase-Transfer Ca-
talyst,” Journal of Molecular Catalysis A: Chemical, Vol.
218, No. 2, 2004, pp. 157-160.
doi:10.1016/j.molcata.2004.04.023
[13] K. Ohkata, J. Kimura, Y. Shinohara, R. Takagi and Y.
Hiraga, “Asymmetric Darzens Condensation of Ketones
with α-Chloroacetates by Means of (–)-8-Phenylmenthyl
Auxiliary,” Chemical Communications, No. 21, 1996, pp.
2411-2412. doi:10.1039/cc9960002411
[14] T. Takahashi, M. Muraoka, M. Capo and K. Koga, “En-
antioselective Darzens Reaction: Asymmetric Synthesis
of Trans-Glycidic Esters Mediated by Chiral Lithium
Amides,” Chemical & Pharmaceutical Bulletin, Vol. 43,
No. 10, 1995, pp. 1821-1823.
[15] R. Ballini and G. Bosica, “Nitroaldol Reaction in Aque-
ous Media: An Important Improvement of the Henry Re-
action,” The Journal of Organic Chemistry, Vol. 62, No.
2, 1997, pp. 425-427. doi:10.1021/jo961201h
[16] B. M. Vanderbilt and H. B. Hass, “Aldehyde-Nitroparaf-
fin Condensation,” Industrial & Engineering Chemistry,
Vol. 32, No. 1, 1940, pp. 34-38.
doi:10.1021/ie50361a007
[17] L. W. Herman and J. W. Apsimon, “A Novel In-
tramolecularly Stabilized Nitronic Acid, 2-Aci-Nitro-
1,3-Propanediol,” Tetrahedron Letters, Vol. 26, No. 11,
1985, pp. 1423-1424.
doi:10.1016/S0040-4039(00)99061-0
[18] V. Simanek, V. Preininger, A. Klasek and J. Jurina, “The
Structure and the Synthesis of Sevanine,” Heterocycles,
Vol. 4, No. 7, 1976, pp. 1263-1267.
doi:10.3987/R-1976-07-1263
[19] A. S. Cavallo, H. Lapitajs, P. Buchert, A. Klein, S. Co-
lonna and A. Manfredi, “Asymmetric Synthesis of Ephe-
drine Analogs,” Journal of Organomettalic Chemistry,
Vol. 330, 1987, pp. 357-363.
[20] D. Seebach, E. W. Colwin, F. Lehr and T. Weller, “Ni-
troaliphatic Compounds-Ideal Intermediates in Organic
Synthesis,” Chimia, Vol. 33, 1979, pp. 1-18.
[21] R. Royer, “Title of This Paper,” Ann. Pharm. Fr., Vol. 41,
No. *, 1983, pp. 299-311.
[22] G. Rossini, R. Ballini and P. Sorrenti, “Synthesis of
2-Nitroalkanols on Alumina Surfaces without Solvent: A
Simple, Mild and Convenient Method,” Synthesis, Vol.
12, 1983, pp. 1014-1016.
[23] J. M. Melot, F. Texier-Boullet and A. Foucaud, “Prepara-
tion and Oxidation of α-Nitro Alcohols with Supported
Copyright © 2011 SciRes. IJOC