Mono- and Bis-Acrolein Derivatives by Reliable and Efficient One-Step Methylenation of Aldehyde Precursors

Abstract

A series of aldehydes carrying different functional groups was transformed directly into the α-methylene derivatives. Dialdehydes behaved comparably at both active sites. When keto aldehydes are involved, excellent levels of chemoselectivity are observed, with the ketone substructures exhibiting no sign of reactivity.

Key words

α,β-unsaturated aldehydes - diethylamine hydrochloride - 1,2-dichloroethane - acroleins - one-step reaction

References

• 1a Blicke FF. Org. React.  1942,  1:  303 
• 1b Hellmann H. Opitz G. Angew. Chem.  1956,  68:  265 
• 1c Reichert B. Die Mannich Reaktion   Springer-Verlag; Berlin: 1959. 
• 1d Hellman H. Opitz G. α-Aminoalkylierung   Verlag Chemie, Weinheim; Germany: 1960. 
• 1e Tramontini M. Synthesis  1973,  703 
• 2 Kinast G. Tietze L.-F. Angew. Chem., Int. Ed. Engl.  1976,  15:  239 
• 3 White JD. Amedio JC. Hrnciar P. Lee NC. Ohira S. Yokochi AFT. Chem. Commun.  1998,  603 
• 4 Paquette LA. Hofferberth JE. J. Org. Chem.  2003,  68:  2265 
• 5a Gras J.-L. Tetrahedron Lett.  1978,  19:  2111 
• 5b Gras J.-L. Tetrahedron Lett.  1978,  19:  2955 
• 6a Farberov MI. Mironov GS. Dokl. Akad. Nauk SSSR  1963,  148:  1095 ; Chem. Abstr. 1963, 59, 5062
• 6b Mironov GS. Farberov MI. Korshunov MA. Uch. Zap. Yaroslavsk. Tekhn. Inst.  1962,  33 ; Chem. Abstr. 1964, 61, 568
• 7 Takano S. Inomata K. Samizu K. Tomita S. Yanase M. Suzuki M. Iwabuchi Y. Sugihara T. Ogasawara K. Chem. Lett.  1989,  1283 
• 8 For a recent synthetic application of such products, consult: Groth U. Jung M. Vogel T. Synlett  2004,  1054