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

Bryan Yong-Hao Tan; Yong-Chua Teo

doi:10.1055/s-0034-1380724

Synlett, Inhaltsverzeichnis

Synlett 2015; 26(12): 1697-1701
DOI: 10.1055/s-0034-1380724

letter

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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Abstract

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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

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Referenzen

References and Notes
1 Gradman AH, Winkle RA, Fitzgerald J, Meffin PJ, Stoner J, Bell PA, Harrison DC. Circulation 1977; 55: 785

2a Scher HI, Kelly WK. J. Clin. Oncol. 1993; 11: 1566
2b McLeod DG, Iversen P, See WA, Morris T, Armstrong J, Wirth MP. BJU international 2006; 97: 247
2c Cabot RC, Harris NL, Rosenberg ES, Shepard J.-AO, Cort AM, Ebeling SH, McDonald EK, Scher HI, Fizazi K, Saad F. N. Engl. J. Med. 2012; 367: 1187

3a Frost F, Jessen B, Siggaard-Andersen J. The Lancet 1980; 315: 499
3b Radwan IA, Saito S, Goto F. Anesth. Analg. 2002; 94: 319

4 Snodin D. J. Org. Process Res. Dev. 2010; 14: 960
5 Erickson J, Dechary J, Kesling M. J. Am. Chem. Soc. 1951; 73: 5301

6a Falk FC, Frohlich R, Paradies J. Chem. Commun. 2011; 47: 11095
6b Ikawa T, Barder TE, Biscoe MR, Buchwald SL. J. Am. Chem. Soc. 2007; 129: 13001
6c Yin J, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 6043

7 Ma F, Xie X, Zhang L, Peng Z, Ding L, Fu L, Zhang Z. J. Org. Chem. 2012; 77: 5279

8a Jammi S, Sakthivel S, Rout L, Mukherjee T, Mandal S, Mitra R, Saha P, Punniyamurthy T. J. Org. Chem. 2009; 74: 1971
8b Xu H, Wolf C. Chem. Commun. 2009; 1715

9a Quan Z.-J, Xia H.-D, Zhang Z, Da Y.-X, Wang X.-C. Appl. Organomet. Chem. 2014; 28: 81
9b Yong F.-F, Teo Y.-C, Chua G.-L, Lim GS, Lin Y. Tetrahedron Lett. 2011; 52: 1169
9c Xiang S.-K, Zhang D.-X, Hu H, Shi J.-L, Liao L.-G, Feng C, Wang B.-Q, Zhao K.-Q, Hu P, Yang H, Yu W.-H. Adv. Synth. Catal. 2013; 355: 1495
9d Lv X, Bao W. J. Org. Chem. 2007; 72: 3863
9e Chen H.-H. Org. Lett. 2006; 8: 5609
9f Klapars A, Huang X, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 7421
9g Tye JW, Weng Z, Johns AM, Incarvito CD, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 9971

10 Beletskaya IP, Cheprakov AV. Coord. Chem. Rev. 2004; 248: 2337
11 Jiang L. Molecules (Basel, Switzerland) 2014; 19: 13448
12 Correa A, Elmore S, Bolm C. Chem. Eur. J. 2008; 14: 3527

13a Teo Y.-C, Chua G.-L. Chem. Eur. J. 2009; 15: 3072
13b Saha P, Ali MA, Ghosh P, Punniyamurthy T. Org. Biomol. Chem. 2010; 8: 5692
13c Toma G, Yamaguchi R. Eur J. Org. Chem. 2010; 2010: 6404

14a Amouri H, Bégué J.-P, Chennoufi A, Bonnet-Delpon D, Gruselle M, Malézieux B. Org. Lett. 2000; 2: 807
14b Braunstein P, Matt D, Nobel D. Chem. Rev. 1988; 88: 747
14c Nicholas KM. Acc. Chem. Res. 1987; 20: 207

15 Tan BY.-H, Teo Y.-C. Org. Biomol. Chem. 2014; 12: 7478
16 Li C.-J, Trost BM. Proc. Natl. Acad. Sci. U.S.A. 2008; 105: 13197
17 Larsson P.-F, Correa A, Carril M, Norrby P.-O, Bolm C. Angew. Chem. Int. Ed. 2009; 48: 5691
18 Allen CL, Williams JM. Chem. Soc. Rev. 2011; 40: 3405

19a Baker JW, Bachman GL, Schumacher I, Roman DP, Tharp AL. J. Med. Chem. 1967; 10: 93
19b Neri RO, Topliss JG. US Patent US4144270, 1979
19c Stabile RG, Dicks AP. J. Chem. Ed. 2003; 80: 1439

20 Bandgar B, Sawant S. Synth. Commun. 2006; 36: 859
21 Ghaffarzadeh M, Rahbar S. J. Chem. Res. 2014; 38: 200

22a Dukes M, Furr BJ, Hughes LR, Tucker H, Woodburn JR. Steroids 2000; 65: 725
22b Labrie F. Cancer 1993; 72: 3816

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.

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