Mild and Efficient Cobalt-Catalyzed Cross-Coupling of Aliphatic Amides and Aryl Iodides in Water

Abstract

A convenient protocol for the C–N cross-coupling of aliphatic amides and iodobenzene is demonstrated using a simple and inexpensive Co(C₂O₄)·2H₂O/N,N′-dimethylethylenediamine (DMEDA) catalytic system in water. Good yields of N-arylated products were isolated (up to 85%) and the protocol has been successfully applied to the synthesis of the anticancer drug, flutamide.

Key words

cobalt - N-arylation - cross-coupling - aliphatic amide - water

• References and Notes

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• 23 General Procedure for N-Arylation of Pyrrolidinone/Aliphatic Amides: A mixture of cobalt(II) oxalate dihydrate (Sigma-Aldrich, 0.294 mmol), Cs₂CO₃ (2.94 mmol), pyrrolidinone or aliphatic amide (1.47 mmol), DMEDA (0.588 mmol), distilled H₂O (0.3 mL) and aryl halide (2.205 mmol) were added to an 8.0-mL reaction vial fitted with a Teflon-sealed screw cap. The reaction mixture was stirred under air in a closed system at 120 °C and 130 °C, respectively for 24 h. The heterogeneous mixture was subsequently cooled to r.t. and diluted with CH₂Cl₂. The combined organic extracts were dried over anhyd Na₂SO₄, filtered and the solvent was removed under reduced pressure. The crude product was loaded into the column using minimal amounts of CH₂Cl₂ and was purified by silica gel column chromatography to afford the N-arylated product. The identity and purity of products were confirmed by ¹H NMR and ¹³C NMR spectroscopic analysis. 1-Phenylpyrrolidin-2-one (2a): off-white solid; 176 mg (75% yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.61 (d, J = 7.7 Hz, 2 H), 7.38 (t, J = 8.0 Hz, 2 H), 7.15 (t, J = 8.0 Hz, 1 H), 3.88 (t, J = 7.0 Hz, 2 H), 2.62 (t, J = 8.0 Hz, 2 H), 2.17 (quin, J = 8.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 182.0, 136.5, 128.9, 124.5, 120.0, 48.8, 32.8, 18.1. HRMS: m/z [M⁺] calcd for C₁₀H₁₁NO: 162.0917; found: 162.0914. 1-(2-Fluorophenyl)pyrrolidin-2-one (2b): off-white solid; 192 mg (73% yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.38–7.43 (m, 1 H), 7.21–7.28 (m, 1 H), 7.10–7.18 (m, 2 H), 3.83 (t, J = 6.8 Hz, 2 H), 2.57 (t, J = 8.4 Hz, 2 H), 2.21 (qn, J = 7.6 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 174.7, 157.0 (d, J = 248.4 Hz), 128.2 (d, J = 7.6 Hz), 127.8 (d, J = 2.3 Hz), 126.3 (d, J = 11.4 Hz), 124.4 (d, J = 3.8 Hz), 116.5 (d, J = 19.8 Hz), 49.9, 31.0, 18.9. HRMS: m/z [M⁺] calcd for C₁₀H₁₀NOF: 180.0822.; found: 180.0806. 1-(3-Methoxyphenyl)pyrrolidin-2-one (2i): pale yellow solid; 169 mg (60% yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.33 (t, J = 2.8 Hz, 1 H), 7.24 (t, J = 8.0 Hz, 1 H), 7.10 (dd, J = 8.0 Hz, 1 H), 6.70 (dd, J = 8.0 Hz, 1 H), 3.82 (t, J = 8.0 Hz, 2 H), 3.80 (s, 3 H), 2.58 (t, J = 8.0 Hz, 2 H), 2.12 (qn, J = 7.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 174.2, 159.9, 140.6, 129.4, 111.9, 110.0, 105.9, 55.2, 48.8, 32.8, 17.9. HRMS: m/z [M⁺] calcd for C₁₁H₁₃NO₂: 192.1022; found: 192.1011. N-[3-(Trifluoromethyl)phenyl]pentanamide (4b): off-white solid; 216 mg (60% yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.81 (s, 1 H), 7.72 (d, J = 9.2 Hz, 1 H), 7.66 (br s, 1 H), 7.40 (t, J = 8.8 Hz, 1 H), 7.34 (d, J = 8.8 Hz, 1 H), 2.38 (t, J = 8.0 Hz, 2 H), 1.70 (qn, J = 8.0 Hz, 2 H), 1.34–1.44 (m, 2 H), 0.93 (t, J = 7.6 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 172.0, 138.5, 131.3 (q, J = 32.8 Hz), 129.5, 123.9 (q, J = 270.6 Hz), 122.9, 120.7 (q, J = 3.4 Hz), 116.6 (q, J = 3.5 Hz), 47.4, 37.6, 22.3, 13.8. HRMS: m/z [M⁺] calcd for C₁₂H₁₄NOF₃: 246.1103; found: 246.1117.