N-Functionalized Amino Acids Promoted Aerobic Copper-Catalyzed Oxidation of Benzylic Alcohols in Water

Abstract

Instead of traditional N,N-bidentate ligands, N-functionlized amino acids were used as powerful N,O-bidentate ligands in aerobic copper/TEMPO-catalyzed system for promoting oxidation of benzylic alcohols. Under the optimized reaction conditions, a wide range of primary and secondary benzylic alcohols have been efficiently converted into aldehydes and ketones with good to excellent yields in water.

Key words

N,O-bidentate ligand - N-functionalized amino acid - copper - alcohol oxidation - benzylic alcohol - water

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• 19 General Procedures for the Copper-Catalyzed Primary Benzylic Alcohol Oxidation under Air in Water (p-Methylbenzyl Alcohol)A mixture of p-methylbenzyl alcohol (1.0 mmol), N-phenylglycine (0.0076 g, 0.05 mmol), CuBr₂ (0.0112 g, 0.05 mmol), Na₂CO₃ (0.1060 g, 1.0 mmol), TEMPO (0.0078 g, 0.05 mmol), H₂O (3.0 mL) were added to a 100 mL Schlenk tube, which was vigorously stirred in air under reflux for 0.5 h. After the reaction, the product was extracted with CH₂Cl₂ (3 × 2.0 mL). The combined organic phase was washed with H₂O (3.0 mL) and dried over anhydrous MgSO₄. After concentration under vacuum, the residue was purified by column chromatography to afford p-methylbenzaldehyde.Isolated yield: 0.1080 g (90%). 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.
• 20 General Procedures for Copper-Catalyzed Secondary Alcohol Oxidation under Reflux in Neat Water (1-Phenethyl Alcohol)A mixture of 1-phenethyl alcohol (1.0 mmol), N-(phenyl)phenylalanine (0.0241 g, 0.1 mmol), CuBr₂ (0.0223 g, 0.1 mmol), NaOAc (0.1640 g, 2.0 mmol), TEMPO (0.0156 g, 0.1 mmol), and H₂O (3.0 mL) were placed into a 100 mL Schlenk tube, which was vigorously stirred in air under reflux for 12 h. After the reaction, the product was extracted with CH₂Cl₂ (3 × 2.0 mL). The combined organic phase was washed with H₂O (3.0 mL) and dried over anhydrous MgSO₄. After concentration under vacuum, the residue was purified by column chromatography to afford acetophenone.Isolated yield: 0.1080 g (90%). 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.