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Synlett 2015; 26(12): 1697-1701
DOI: 10.1055/s-0034-1380724
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© Georg Thieme Verlag Stuttgart · New York

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

Bryan Yong-Hao Tan
Natural Sciences and Science Education, National Institute of Education, Nanyang Technological University, 1 Nanyang Walk, 637616, Singapore   eMail: yongchua.teo@nie.edu.sg
,
Yong-Chua Teo*
Natural Sciences and Science Education, National Institute of Education, Nanyang Technological University, 1 Nanyang Walk, 637616, Singapore   eMail: yongchua.teo@nie.edu.sg
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Publikationsverlauf

Received: 02. April 2015

Accepted after revision: 14. April 2015

Publikationsdatum:
01. Juni 2015 (online)

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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

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380724.
  • Supporting Information
 

  • 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.