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B. Basu et al.
LETTER
(10) General Procedure for the Amination Reactions:
References
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.
(1) (a) Iwaki, T.; Yasuhara, A.; Sakamoto, T. J. Chem. Soc.,
Perkin Trans. 1 1999, 1505. (b) Negwer, M. Organic
Chemical Drugs and their Synonyms (International Survey),
7th Ed; Akademie Verlag Gmbh: Berlin, 1994.
(c) D’Aproano, G.; Schiavon, G.; Leclerc, M. Chem. Mater.
1995, 7, 33. (d) Sadighi, P.; Singer, R. A.; Buchwald, S. L.
J. Am. Chem. Soc. 1998, 120, 4960. (e) MacDiarmid, A. G.;
Epstein, A. J. In Science and Applications of Conducting
Polymers; Salaneck, W. R.; Clark, D. T.; Samuelsen, E. J.,
Eds.; Hilger: New York, 1991, 117. (f) Kanbara, T.;
Miyazaki, Y.; Hasegawa, K.; Yamamoto, T. J. Polym. Sci.
Part A: Polym. Chem. 2000, 38, 4194. (g) Greco, G. E.;
Popa, A. I.; Schrock, R. R. Organometallics 1998, 17, 5591.
(2) For reviews: (a) Wolfe, J. P.; Wagaw, S.; Marcoux, J. F.;
Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805. (b) Muci,
A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219, 133.
(c) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1996, 61,
1133. (d) Guram, A. S.; Rennels, R. A.; Buchwald, S. L.
Angew. Chem., Int. Ed. Engl. 1995, 34, 1348. (e)Guram, A.
S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901.
(3) For reviews: (a) Hartwig, J. F. Pure Appl. Chem. 1999, 71,
1417. (b) Hartwig, J. F. Acc. Chem. Res. 1998, 31, 852.
(c) Hartwig, J. F. Synlett 1997, 329. (d) Hartwig, J. F.;
Kawatsura, M.; Hauck, S. I.; Shaughnessy, K.; Alcazar-
Roman, L. M. J. Org. Chem. 1999, 64, 5575. (e) Paul, F.;
Patt, J.; Hartwig, J. F. J. Am. Chem. Soc. 1994, 116, 5969.
(4) Smith, M. B.; March, J. In March’s Advanced Organic
Chemistry, 5th Ed.; John Wiley & Sons: New York, 2001,
850–893.
(11) Selected Spectral Data for Mono- and Bis-Coupled
Products
Table 1, Entry 5: 1-(4-Piperidin-1-yl-phenyl)ethanone:
IR (Nujol): 1675, 1206.5 cm–1. 1H NMR (CDCl3, 300 MHz):
d = 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): d = 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): d = 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): d = 24.4, 26.0, 51.2, 106.1, 108.7, 129.3,
153.2.
(5) (a) Ferreira, I. C. F. R.; Queiroz, M.-J. R. P.; Kirsch, G.
Tetrahedron 2003, 59, 975. (b) Grasa, G. A.; Mihai, S. V.;
Huang, J.; Nolan, S. P. J. Org. Chem. 2001, 66, 7729.
(c) Parrish, C. A.; Buchwald, S. L. J. Org. Chem. 2001, 66,
3820. (d) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1997,
62, 6066. (e) Ma, D.; Yao, J. Tetrahedron: Asymmetry 1996,
7, 3075. (f) Frost, C. G.; Mendonca, P. J. Chem. Soc., Perkin
Trans. 1 1998, 2615. (g) Hartwig, J. F. In Modern
Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim,
2002.
Table 1, Entry 11: 1,4-Dimorpholino Benzene: IR
(Nujol): 1234.4, 1120.6 cm–1. 1H NMR (CDCl3, 300 MHz):
d = 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): d = 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-d6, 300 MHz): d = 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). 13
C
(6) (a) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 2000, 65,
1144. (b) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37,
2046.
NMR (acetone-d6, 75MHz): d = 34.7, 48.6, 63.9, 107.5,
117.9.
(7) (a) Singer, R. A.; Sadighi, J. P.; Buchwald, S. L. J. Am.
Chem. Soc. 1998, 120, 213. (b) Goodson, F. E.; Hauck, S. I.;
Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 7527.
(c) Kanbara, T.; Izumi, K.; Narise, T.; Hasegawa, K. Polym.
J. 1998, 30, 66.
(8) (a) Rivas, F. M.; Riaz, U.; Diver, S. T. Tetrahedron:
Asymmetry 2000, 11, 1703. (b) Beletskaya, L.;
Bessmertnykh, A. G.; Guilard, R. Tetrahedron Lett. 1999,
40, 6393.
(9) Basu, B.; Jha, S.; Mridha, N. K.; Bhuiyan, M. M. H.
Tetrahedron Lett. 2002, 43, 7967.
Table 1, Entry 15: (2-Bromophenyl)cyclohexylamine: IR
(Nujol): 1321.1, 1016.4 cm–1. 1H NMR (CDCl3, 300 MHz):
d = 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). 13
C
NMR (CDCl3, 75 MHz ): d = 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): d = 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 ): d = 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):
d = 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): d =
24.3, 26.0, 51.5, 99.2, 153.7.
Synlett 2005, No. 8, 1275–1278 © Thieme Stuttgart · New York