An Efficient Biomimetic Aerobic Oxidation of Alcohols Catalyzed by Iron Combined with Amino Acids

Abstract

A novel combination of FeCl₃, l-valine and TEMPO is found to oxidize alcohols to the carbonyl compounds with dioxygen. A wide range of primary/secondary benzyl, allylic, and heterocyclic alcohols have been efficiently converted into aldehydes and ketones with good to excellent isolated yields.

Key words

alcohols - aldehydes - amino acids - iron - ketones - oxidation

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• 25 Typical Procedure for Primary Alcohol Oxidation (p-Methylbenzyl Alcohol) A mixture of p-methylbenzyl alcohol (0.1222 g, 1.0 mmol), l-valine (0.0117 g, 0.1 mmol), FeCl₃ (0.0081 g, 0.05 mmol), TEMPO (0.0156 g, 0.1 mmol), toluene (4.0 mL), 4 Å MS (0.7000 g) were added to a 150 mL Schlenk tube. Then the resulting mixture was vigorously stirred under oxygen at reflux temperature for 12 h. After the reaction, the residue was filtered off, and the solvent was removed under vacuum to give the crude product, which was purified by column chromatography on silica gel to give the pure product 1 (0.1093 g isolated yield 91%). ¹H NMR (500 MHz, CDCl₃): δ = 2.38 (s, 3 H), 7.27 (d, J = 4.3 Hz, 2 H), 7.73 (d, J = 4.0 Hz, 2 H), 9.91 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.5, 129.4, 129.5, 134.0, 145.2, 191.6.
• 26 Typical Procedure for Secondary Alcohol Oxidation (1-Phenethyl Alcohol) A mixture of 1-phenethyl alcohol (0.1222 g, 1.0 mmol), l-valine (0.0117 g, 0.1 mmol), FeCl₃ (0.0162 g, 0.1 mmol), TEMPO (0.0156 g, 0.1 mmol), toluene (4.0 mL), 4 Å MS (0.7000 g) were added to a 150 mL Schlenk tube. Then the resulting mixture was vigorously stirred under oxygen at reflux temperature for 24 h. After the reaction, the residue was filtered off, and the solvent was removed under vacuum to give the crude product, which was purified by column chromatography on silica gel to give the pure product 26 (0.1093 g isolated yield 91%). ¹H NMR (500 MHz, CDCl₃): δ = 2.52 (s, 3 H), 7.40 (t, J = 7.5 Hz, 2 H), 7.51 (t, J = 7.0 Hz, 1 H), 7.91 (d, J = 4.3 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 26.5, 128.2, 128.5, 133.0, 137.1, 198.1.