Synthesis of 3-Alkyl-2,5-dimethylfuran Derivatives by Indirect Alkylation of 2,5-Dimethylfuran with Aliphatic Nitrocompounds

Abstract

The preparation of 3-alkyl-2,5-dimethylfuranes via indirect alkylation of 2,5-dimethylfuran is reported. Thus, primary nitroalkanes react with cis-3-hexen-2,5-dione giving a tandem Michael addition/elimination of nitrous acid, followed by chemoselective hydrogenation of the C=C double bond of the obtained enones. The Paal-Knorr reaction, performed with p-toluenesulfonic acid in diethyl ether, completes the formation of the title compounds. In this context the nitroalkane can be considered as an alkyl cation synthon.

furan - nitroalkanes - Michael reaction - heterocyclization

References

1 Bosshard P. Eugster CH. In Advances in Heterocyclic Chemistry   Vol. 7:  Katritzky AR. Boulton AJ. Academic Press; New York: 1966.  p.377-488  

2a Livingstone R. In Rodd’s Chemistry of Carbon Compounds   Part A, Vol. IV:  Coffey S. Elsevier; Amsterdam: 1973.  p.83-217  

2b Dean FM. In Advances in Hetrocyclic Chemistry   Part I, Vol. 30:  Katritzky AR. Academic Press; New York: 1982.  p.167-238  

2c Acheson RM. An Introduction to the Chemistry of Heterocyclic Compounds   Wiley; Toronto: 1976. 

3 Lipshutz BH. Chem. Rev.  1986,  86:  795 

4 Nakanishi K. Natural Products Chemistry   Kodansha Ltd; Tokyo: 1974. 

5a Hou XL. Cheung HY. Hon TY. Kwan PL. Lo TH. Tong SY. Wong HNC. Tetrahedron  1998,  54:  1955 

5b Aurrecoechea JM. Pèrez E. Solay M. J. Org. Chem.  2001,  66:  564 

6 Rosini G. Ballini R. Synthesis  1988,  833 

7 Ballini R. Rinaldi A. Tetrahedron Lett.  1994,  35:  9247 

8a Ballini R. Bosica G. Tetrahedron  1995,  51:  4213 

8b Ballini R. Bosica G. Petrelli L. Petrini M. Synthesis  1999,  1236 

8c Ballini R. Marcantoni E. Perella S. J. Org. Chem.  1999,  64:  2954 

8d Ballini R. Bosica G. Masè A. Petrini M. Eur. J. Org. Chem.  2000,  2927 , and references cited therein

9 Dominguez C. Czàky AG. Plumet J. Tetrahedron Lett.  1990,  31:  7669 

10 Friedrichsen W. In Furans and their Benzo Derivatives   Vol. 2:  Katritzky AR. Rees CW. Scriven EFV. Pergamon; Elsevier Science Ltd: Oxford: 1996.  p.352 

11 Scott LT. Naples JO. Synthesis  1973,  209 

12 Traynelis VJ. Hergenrother WI. Hanson HT. Valicenti JA. J. Org. Chem.  1964,  29:  123