Anodic Cyanation of β-Dicarbonyl Compounds

Abstract

Several β-dicarbonyl compounds were electrochemically oxidized in a methanolic solution in the presence of sodium cyanide and sodium methoxide to yield the corresponding α-cyano-β-dicarbonyl compounds in moderate to good yields. Presumably, a two-electron transfer transforms the anion derived from the β-dicarbonyl compounds into a cation, which then reacts with a cyanide ion to afford the cyanation products.

Key words

oxidation - ketones - esters - nitriles - cations

References

• For example, see:
• 1a Torii S. Electroorganic Synthesis   Kodansha; Tokyo: 1985. 
• 1b Weinberg NL. Technique of Electroorganic Synthesis   Wiley-Interscience; New York: 1975. 
• 1c Shono T. Tetrahedron  1984,  40:  811 
• 1d Okimoto M. Takahashi Y. Curr. Org. Synth.  2004,  1:  233 
• 2a Brettle R. Parkin JG. J. Chem. Soc. C  1967,  1352 
• 2b Okudo T. Tsutsumi S. Bull. Chem. Soc. Jpn.  1964,  37:  1794 
• 2c Schäfer HJ. Angew. Chem.  1981,  93:  978 
• 3a Yoshida K. Fueno T. J. Org. Chem.  1972,  37:  4145 
• 3b Chiba T. Takata Y. J. Org. Chem.  1977,  42:  2973 
• 3c Andreades S. Zahnow EW. J. Am. Chem. Soc.  1969,  91:  4181 
• 4a Okimoto M. Chiba T. J. Org. Chem.  1988,  53:  218 
• 4b Okimoto M. Chiba Y. J. Org. Chem.  1990,  55:  1070 
• 4c Chiba T. Okimoto M. Chem. Lett.  1993,  521 
• 4d Okimoto M. Chiba T. J. Org. Chem.  1993,  58:  6194 
• 4e Okimoto M. Takahashi Y. Kakuchi T. Synthesis  2003,  2057 
• 5a Okimoto M. Takahashi Y. Synthesis  2002,  2215 
• 5b Okimoto M. Takahashi Y. Nagata Y. Sasaki G. Numata K. Synthesis  2005,  705 
• 5c Okimoto M. Takahashi Y. Bull. Chem. Soc. Jpn.  2003,  76:  427 
• 6 Beilsteins Handbuch der Organischen Chemie   4th ed.:  Springer; Berlin: 1943.