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.

carboxylic acids - esters - ketones - oxidations - ring opening

References

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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.

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