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

Wei Xu; Yuyang Jiang; Hua Fu

doi:10.1055/s-0031-1290302

Synlett, Table of Contents

Synlett 2012; 23(5): 801-804
DOI: 10.1055/s-0031-1290302

letter

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

Wei Xu

^aKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China

,

Yuyang Jiang

^bKey Laboratory of Chemical Biology (Guangdong Province), Graduate School of Shenzhen, Tsinghua University, Shenzhen 518057, P. R. of China, Fax: +86(10)62781695 Email: fuhua@mail.tsinghua.edu.cn

,

Hua Fu*

^aKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China

^bKey Laboratory of Chemical Biology (Guangdong Province), Graduate School of Shenzhen, Tsinghua University, Shenzhen 518057, P. R. of China, Fax: +86(10)62781695 Email: fuhua@mail.tsinghua.edu.cn

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Abstract

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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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References

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15 K₂CO₃ (99.997%), Mg (2 ppm), Na (8 ppm), other elements including Al, Sb, As, Ba, Bi, B, Cd, Ca, Cr, Co, Cu, In, Fe, Pb, Li, Mn, Mo, Ni, P, Si, Te, Sn, Ti, V, Zn, Zr (sought but not detected). The data were provided by Alfa Aesar
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) ¹⁷Eluent: 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) ¹⁷Eluent: 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]⁺
17 Owston NA, Parker AJ, Williams JM. J. Org. Lett. 2007; 9: 73

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