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Synlett 2005(8): 1275-1278  
DOI: 10.1055/s-2005-865241
LETTER
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Selective Amination of Haloaromatics on KF-Alumina Surface

Basudeb Basu*, Pralay Das, Ashish K. Nanda, Sajal Das, Sajal Sarkar
Department of Chemistry, University of North Bengal, Darjeeling 734 430, India
Fax: +91(353)2581546; e-Mail: basu_nbu@indiatimes.com;
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Publication History

Received 10 December 2004
Publication Date:
21 April 2005 (online)

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Abstract

An efficient palladium-catalyzed amination, including polyaminations of aromatic bromides mediated on a surface of KF-alumina, is reported. The solvent-free one-pot protocol avoids the use of a strong base (sodium tert-butoxide) making it applicable to substrates containing a base-sensitive functional group. It proceeds without concomitant reductive bromination and provides access to selective amination of polyhaloaromatics.

Key words

aryl halides - aryl amines - amination - palladium - KF-alumina

    References

  • 1a Iwaki T. Yasuhara A. Sakamoto T. J. Chem. Soc., Perkin Trans. 1  1999,  1505 
  • 1b Negwer M. Organic Chemical Drugs and their Synonyms (International Survey)   7th Ed:  Akademie Verlag Gmbh; Berlin: 1994. 
  • 1c D’Aproano G. Schiavon G. Leclerc M. Chem. Mater.  1995,  7:  33 
  • 1d Sadighi P. Singer RA. Buchwald SL. J. Am. Chem. Soc.  1998,  120:  4960 
  • 1e MacDiarmid AG. Epstein AJ. In Science and Applications of Conducting Polymers   Salaneck WR. Clark DT. Samuelsen EJ. Hilger; New York: 1991.  p.117 
  • 1f Kanbara T. Miyazaki Y. Hasegawa K. Yamamoto T. J. Polym. Sci. Part A: Polym. Chem.  2000,  38:  4194 
  • 1g Greco GE. Popa AI. Schrock RR. Organometallics  1998,  17:  5591 
  • For reviews:
  • 2a Wolfe JP. Wagaw S. Marcoux JF. Buchwald SL. Acc. Chem. Res.  1998,  31:  805 
  • 2b Muci AR. Buchwald SL. Top. Curr. Chem.  2002,  219:  133 
  • 2c Wolfe JP. Buchwald SL. J. Org. Chem.  1996,  61:  1133 
  • 2d Guram AS. Rennels RA. Buchwald SL. Angew. Chem., Int. Ed. Engl.  1995,  34:  1348 
  • 2e Guram AS. Buchwald SL. J. Am. Chem. Soc.  1994,  116:  7901 
  • For reviews:
  • 3a Hartwig JF. Pure Appl. Chem.  1999,  71:  1417 
  • 3b Hartwig JF. Acc. Chem. Res.  1998,  31:  852 
  • 3c Hartwig JF. Synlett  1997,  329 
  • 3d Hartwig JF. Kawatsura M. Hauck SI. Shaughnessy K. Alcazar-Roman LM. J. Org. Chem.  1999,  64:  5575 
  • 3e Paul F. Patt J. Hartwig JF. J. Am. Chem. Soc.  1994,  116:  5969 
  • 4 Smith MB. March J. In March’s Advanced Organic Chemistry   5th Ed.:  John Wiley & Sons; New York: 2001.  p.850-893  
  • 5a Ferreira ICFR. Queiroz M.-JRP. Kirsch G. Tetrahedron  2003,  59:  975 
  • 5b Grasa GA. Mihai SV. Huang J. Nolan SP. J. Org. Chem.  2001,  66:  7729 
  • 5c Parrish CA. Buchwald SL. J. Org. Chem.  2001,  66:  3820 
  • 5d Wolfe JP. Buchwald SL. J. Org. Chem.  1997,  62:  6066 
  • 5e Ma D. Yao J. Tetrahedron: Asymmetry  1996,  7:  3075 
  • 5f Frost CG. Mendonca P. J. Chem. Soc., Perkin Trans. 1  1998,  2615 
  • 5g Hartwig JF. In Modern Amination Methods   Ricci A. Wiley-VCH; Weinheim: 2002. 
  • 6a Wolfe JP. Buchwald SL. J. Org. Chem.  2000,  65:  1144 
  • 6b Hartwig JF. Angew. Chem. Int. Ed.  1998,  37:  2046 
  • 7a Singer RA. Sadighi JP. Buchwald SL. J. Am. Chem. Soc.  1998,  120:  213 
  • 7b Goodson FE. Hauck SI. Hartwig JF. J. Am. Chem. Soc.  1999,  121:  7527 
  • 7c Kanbara T. Izumi K. Narise T. Hasegawa K. Polym. J.  1998,  30:  66 
  • 8a Rivas FM. Riaz U. Diver ST. Tetrahedron: Asymmetry  2000,  11:  1703 
  • 8b Beletskaya L. Bessmertnykh AG. Guilard R. Tetrahedron Lett.  1999,  40:  6393 
  • 9 Basu B. Jha S. Mridha NK. Bhuiyan MMH. Tetrahedron Lett.  2002,  43:  7967 
10

General Procedure for the Amination Reactions:
A: A mixture of Pd2 (dba)3 (2 mol%) and BINAP (4 mol%) was admixed intimately with KF-Alumina (2:3; 2 g) and heated at 80-90 °C for 15 min. Aryl bromide (2 mmol) and amine (5 mmol) were added to the solid surface and the mixture was stirred at 80-90 °C for 1 h. An orange color developed while mixing and gradually disappeared over 1 h. The solid mass was then cooled, packed on a column of silica gel and eluted with EtOAc-light petroleum (1:19) to afford the mono-aryl amines. All the products were identified by IR, 1H and 13C NMR spectral data.
Condition B: The reaction conditions were identical except the quantity of amine was increased to 7-8 equiv, KF-alumina was used in the ratio of 3:2, and the solid mixture was heated at 135 °C for 3 h. Pure bis-amines were obtained by chromatography over silica gel and elution with EtOAc-light petroleum (1:9). The spectral data were consistent with the assigned structures.

11

Selected Spectral Data for Mono- and Bis-Coupled ProductsTable 1, Entry 5: 1-(4-Piperidin-1-yl-phenyl)ethanone: IR (Nujol): 1675, 1206.5 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 1.65 (m, 6 H), 2.50 (s, 3 H), 3.34 (m, 4 H), 6.84 (d, 2 H, J = 9.0 Hz), 7.85 (d, 2 H, J = 9.0 Hz). 13C NMR (CDCl3, 75 MHz): δ = 24.3, 25.3, 26.0, 48.6, 113.3, 126.7, 130.5, 154.4, 196.4.
Table 1, Entry 7: 1, 3-Dipiperidino Benzene: IR (Nujol): 1201.6, 1124.4 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 1.55-1.62 (m, 4 H), 1.70-1.78 (m, 8 H), 3.16 (t, 8 H, J = 5.4 Hz), 6.49 (dd, 2 H, J = 8.1, 2.2 Hz), 6.61 (s, 1 H), 7.15 (m, 1 H). 13C NMR (CDCl3, 75 MHz): δ = 24.4, 26.0, 51.2, 106.1, 108.7, 129.3, 153.2.
Table 1, Entry 11: 1,4-Dimorpholino Benzene: IR (Nujol): 1234.4, 1120.6 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 3.01 (t, 8 H, J = 4.7 Hz), 3.80 (t, 8 H, J = 4.7 Hz), 6.85 (s, 4 H). 13C NMR (CDCl3, 75 MHz): δ = 50.5, 66.9, 117.4, 145.8.
Table 1, Entry 13: 1,4-Di-[8-(1,4-dioxa-8-aza-spiro[4,5]decane)]benzene: IR (Nujol): 1125 cm-1. 1H NMR (acetone-d 6, 300 MHz): δ = 1.76 (t, 8 H, J = 5.7 Hz), 3.16 (t, 8 H, J = 5.7 Hz), 3.94 (s, 8 H), 6.88 (s, 4 H). 13C NMR (acetone-d 6, 75MHz): δ = 34.7, 48.6, 63.9, 107.5, 117.9.
Table 1, Entry 15: (2-Bromophenyl)cyclohexylamine: IR (Nujol): 1321.1, 1016.4 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 1.20-1.44 (m, 6 H), 1.75-1.79 (m, 2 H), 2.02-2.1 (m, 2 H), 3.30 (m, 1 H), 4.26 (br s, 1 H), 6.5 (m, 1 H), 6.6 (d, 1 H, J = 8.1 Hz), 7.14 (m, 1 H), 7.40 (d, 1 H, J = 8.8 Hz). 13C NMR (CDCl3, 75 MHz ): δ = 24.8, 25.8, 33.0, 51.6, 109.8, 111.8, 117.1, 128.3, 132.5, 144.
Table 1, Entry 17: 8-(10-Bromoanthracene-9-yl)-1,4-dioxa-8-aza-spiro[4,5]decane: IR (Nujol): 1122.5 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 2.05 (t, 4 H, J = 5.3 Hz), 3.57 (t, 4 H, J = 5.3 Hz), 4.10 (s, 4 H), 7.48-7.60 (m, 4 H), 8.48 (d, 2 H, J = 8.7 Hz), 8.56 (d, 2 H, J = 8.7 Hz). 13C NMR (CDCl3, 75 MHz ): δ = 36.4, 49.9, 64.4, 107.6, 125.2, 125.3, 126.9, 128.3, 131.2, 131.4, 134.1, 145.3.
Table 1, Entry 19: 1,3,5-Tripiperidino Benzene: IR (Nujol): 1199.6, 1122.5 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 1.51-1.58 (m, 6 H), 1.66-1.73 (m, 12 H), 3.10 (t, 12 H, J = 5.3 Hz), 6.14 (s, 3 H). 13C NMR (CDCl3, 75 MHz): δ = 24.3, 26.0, 51.5, 99.2, 153.7.