Synthesis of α,ω-Dicarboxylic Acid Dimethyl Esters from Cycloalkanones

Abstract

Reaction of cycloalkanones with [hydroxy(2,4-dinitrobenzenesulfonyloxy)iodo]benzene and subsequent treatment of α-[(2,4-dinitrobenzene)sulfonyl]oxy cycloalkanone intermediates with Oxone^® and PTSA in MeOH-H₂O (6:1, v/v) solution provided dicarboxylic acid dimethyl esters in high yields.

Key words

carboxylic acids - esters - ketones - oxidations - ring opening

References

• 1 Ballini R. Bosica G. Tetrahedron  1997,  53:  16131 ; and quoted references
• 2 Feuer H. Pivawer PM. J. Org. Chem.  1969,  34:  2917 
• 3 He L. Horiuchi CA. Bull. Chem. Soc. Jpn.  1999,  72:  2515 
• 4 Kirihara M. Takizawa S. Momose T. J. Chem. Soc., Perkin Trans. 1  1998,  7 
• 5a Fischer RH. Weitz HM. Synthesis  1980,  261 
• 5b Stach H. Hesse M. Tetrahedron  1988,  44:  1573 
• 5c Rathore R. Lin Z. Kochi JK. Tetrahedron Lett.  1993,  34:  1859 
• 5d Rathore R. Kochi JK. J. Org. Chem.  1996,  61:  627 
• 5e Ballini R. Synlett  1999,  1009 
• 5f Shahi SP. Gupta A. Pitre SV. Venkat Ram Reddy M. Kumareswaran R. Vankar YD. J. Org. Chem.  1999,  64:  4509 
• 6a Griswold AA. Starcher PS. J. Org. Chem.  1966,  31:  357 
• 6b Fischer RH. Weitz HM. Liebigs Ann. Chem.  1979,  612 
• 7 Hirao T. Mori M. Ohshiro Y. Bull. Chem. Soc. Jpn.  1989,  62:  2399 
• 8a Lee JC. Oh YS. Cho SH. Bull. Korean Chem. Soc.  1996,  17:  989 
• 8b Lee JC. Choi J.-H. Lee YC. Synlett  2001,  1563 
• 10 Koser GF. Aldrichmica Acta  2001,  34:  89 

9

General experimental procedure: To a solution of ketone (1.0 mmol) in 20 mL of acetonitrile, [hydroxy(2,4-dinitrobenzenesulfonyloxy)iodo]benzene (HDNIB, 0.70 g, 1.5 mmol) was added and the reaction mixture was stirred for 1 h at reflux. The solvent was removed under reduced pressure. The resulting residue was dissolved in methanol (30 mL) and H₂O (5 mL). To the reaction solution, Oxone^® (1.35 g, 2.20 mmol) and PTSA (0.19 g, 1.0 mmol) were added and the mixture was stirred for 2 h at 65 °C. The reaction mixture was filtered through pad of Celite, and organic solvent in filtrate was evaporated and the residue was extracted with ethyl acetate (2 × 30 mL), washed with H₂O (2 × 20 mL), and dried over MgSO₄. After evaporation of solvent, the residue was purified by flash column chromatography (SiO₂, ethyl acetate-hexane = 1:3) to give desired diester.