Copper-Catalyzed Aerobic Oxidative Synthesis of Primary Amides from (Aryl)methanamines

Abstract

A copper-catalyzed aerobic oxidative method for the synthesis of primary aryl amides has been developed, and the direct oxygenation of (aryl)methanamines to primary aryl amides by molecular oxygen showed convenient, practical, and environment-friendly advantages. This method will find wide application in chemistry and biology.

Key words

copper - (aryl)methanamine - aryl amide - aerobic oxidation - synthetic method

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• 16 General Procedure for the Synthesis of Compounds 2a–l A 25 mL Schlenk tube was charged with a magnetic stirrer, (aryl)methanamine (1, 0.5 mmol), K₂CO₃ (1 mmol, 138 mg), and CuBr (0.1 mmol, 14 mg) in mixed solvent of DMSO (2 mL) and H₂O (40 μL). The mixture was allowed to stir under O₂ (1 atm) at 140–160 °C for 6–12 h (see Table 2 for details). After completion of the reaction, the resulting solution was cooled to r.t. and filtered, and the solvent of filtrate was removed with the aid of a rotary evaporator. The residue was purified by column chromatography on silica gel using PE–EtOAc as eluent to provide the desired product 2. Analytical Data for Two Typical Examples 3-Pyridinecarboxamide (2i) ¹⁷ Eluent: EtOAc; yield 55 mg (90%); white solid; mp 131–132 °C (lit.17 131–132 °C). ¹H NMR (300 MHz, DMSO-d ₆): δ = 9.09 (s, 1 H), 8.74 (d, 1 H, J = 4.1 Hz), 8.26 (d, 2 H, J = 8.3 Hz), 7.68 (s, 1 H), 7.53 (dd, 1 H, J = 4.8, 4.8 Hz). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 166.5, 151.9, 148.7, 135.3, 129.7, 123.5. ESI-MS: m/z = 123.4 [M + H]⁺. 2-Furancarboxamide (2k) ¹⁷ Eluent: PE–EtOAc (1:1); yield 42 mg (76%); white solid; mp 140–142 °C (lit.17 140–142 °C). ¹H NMR (300 MHz, DMSO-d ₆): δ = 7.81 (s, 1 H), 7.76 (s, 1 H), 7.37 (s, 1 H), 7.10 (d, 1 H, J = 3.4 Hz), 6.60 (dd, 1 H, J = 1.7, 1.7 Hz). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 159.4, 148.0, 145.0, 113.6, 111.8. ESI-MS: m/z = 112.5 [M + H]⁺
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