T. Kubo et al. / Tetrahedron 64 (2008) 11230–11236
11235
under argon atmosphere to prevent absorption of moisture. CuI
Supplementary data
(99.5% purity) and CsOAc (95% purity) were purchased from Wako
Pure Chemical Industries, Ltd. and were used as-supplied. Dry
DMSO was purchased from Aldlich Chemical Co. and was used as-
supplied.
Detailed experimental procedure containing preparation of
substrates and spectroscopic data. Supplementary data associated
with this article can be found in the online version, at doi:10.1016/
4.2. General procedure for the catalytic intramolecular aryl
amination with N-nosyl-2-bromophenylethylamine (4c)
References and notes
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2006, 25, 82; (v) Strieter, E. R.; Buchwald, S. L. Angew. Chem., Int. Ed. 2006, 45, 925;
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Ikawa, T.; Barder, T. E.; Biscoe, M. R.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129,
13001; (z) Biscoe, M. R.; Barder, T. E.; Buchwald, S. L. Angew. Chem., Int. Ed. 2007, 46,
7232; For reviews, see: (aa) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999,
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L.; Buchwald, S. L.; Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; Wiley-VCH:
Weinheim, 2004; Vol. 2, pp 699–760.
An oven-dried round-bottomed flask was charged with CsOAc
(3.75 g, 19.5 mmol, 2.5 equiv), CuI (14.9 mg, 78.1 mmol, 1.0 mol %),
and N-nosyl-2-bromophenylethylamine (4c) (3.01 g, 7.81 mmol,
1.0 equiv). The flask was evacuated and backfilled with argon. To
the mixture was added dry DMSO (39 mL). The reaction mixture
was stirred at 90 ꢀC for 24 h. After cooling to room temperature, to
the resulting mixture were added ethyl acetate and ammoniacal
aqueous NaCl. The mixture was shaken vigorously to dissolve the
precipitate, then extracted three times with ethyl acetate. The
combined organic extracts were dried over sodium sulfate, filtered,
and concentrated under reduced pressure. The crude material was
purified by column chromatography to afford N-nosylindoline (5c)
(2.30 g, 7.56 mmol, 97%) as a white solid. 1H NMR (400 MHz,
CDCl3):
d
7.93 (dd, J¼8.2, 1.2 Hz, 1H), 7.68 (td, J¼7.6, 1.2 Hz, 1H),
7.61–7.57 (m, 2H), 7.45 (d, J¼8.0 Hz, 1H), 7.18 (td, J¼8.2, 0.9 Hz, 2H),
7.02 (td, J¼7.6, 0.9 Hz, 1H), 4.14 (t, J¼7.0 Hz, 2H), 3.07 (t, J¼8.4 Hz,
2H). 13C NMR (100 MHz, CDCl3):
d 148.3, 141.0, 134.0, 131.7, 131.6,
131.4, 130.0, 127.7, 125.4, 124.2, 124.1, 114.4, 50.3, 27.9. IR (neat,
cmꢁ1): 3095, 2905, 1592, 1543, 1478, 1460, 1440, 1367, 1244, 169,
1126, 1106, 1064, 1028, 981, 851, 745. Anal. Calcd for C14H12N2O4S:
N, 9.21; C, 55.25; H, 3.97. Found: N, 8.99; C, 55.36; H, 4.21.
4.3. General procedure for the catalytic intermolecular aryl
amination of iodobenzene and n-butylamine
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Hartwig, J. F. J. Am. Chem. Soc. 1997, 119, 8232; (i) Hamann, B. C.; Hartwig, J. F.
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852; (l) Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-
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(n) Stauffer, S. R.; Lee, S.; Stambuli, J. P.; Hauck, S. I.; Hartwig, J. F. Org. Lett. 2000, 2,
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Arene Chemistry; Wiley-VCH: Weinheim, 2002; p 107.
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(b) Klapars, A.; Antilla, J. C.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2001,
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Buchwald, S. L. Org. Lett. 2002, 4, 581; (g) Kwong, F. Y.; Buchwald, S. L. Org. Lett.
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(n) Altman, R. A.; Buchwald, S. L. Org. Lett. 2007, 9, 643; (o) Martin, R.; Larsen, C.
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An oven-dried round-bottomed flask was charged with CsOAc
(9.66 g, 50.3 mmol, 2.0 equiv) and CuI (478 mg, 2.51 mmol, 10 mol
%). The flask was evacuated and backfilled with argon. To the
mixture were added iodobenzene (2.80 mL, 25.1 mmol, 1.0 equiv),
n-BuNH2 (3.73 mL, 37.7 mmol, 1.5 equiv), and dry DMSO (25 mL).
The reaction mixture was stirred at 90 ꢀC for 24 h. After cooling to
room temperature, to the resulting mixture were added ethyl ac-
etate and ammoniacal aqueous NaCl. The mixture was shaken
vigorously to dissolve the precipitate and then extracted twice with
ethyl acetate. The combined organic extracts were washed with
brine, dried over sodium sulfate, filtered, and concentrated under
reduced pressure. The crude material was purified by column
chromatography to afford N-butylaniline (14) (3.34 g, 22.4 mmol,
89%) as a colorless oil. 1H NMR (400 MHz, CDCl3):
d 7.17 (t, 2H,
J¼7.6 Hz), 6.68 (t, 1H, J¼7.6 Hz), 6.60 (d, 2H, J¼7.6 Hz), 3.57 (br s,
1H), 3.11 (t, 2H, J¼7.1 Hz), 1.60 (tt, 2H, J¼7.1, 7.1 Hz), 1.43 (tq, 2H,
J¼7.3, 7.1 Hz), 0.96 (t, 3H, J¼7.3 Hz). 13C NMR (100 MHz, CDCl3):
d
148.5, 129.2, 117.0, 112.7, 43.6, 31.7, 20.3, 13.9. IR (neat, cmꢁ1):
3410, 3052, 3020, 2957, 2930, 2871, 1604, 1506, 1478, 1430, 1321,
1264, 1179, 1153, 992, 867, 748, 692. HRMS-FAB cacld for C10H16
N
(MþþH), 150.1282; found 150.1283.
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Acknowledgements
This work was financially supported by
a Grant-in-Aid
(15109001, 17689003, 20390003) from the Ministry of Education,
Culture, Sports, Science, and Technology, Japan, Kato Memorial
Bioscience Foundation, Takeda Science Foundation, and JSPS (pre-
doctoral fellowship for K.O.).
6. (a) Yamada, K.; Kubo, T.; Tokuyama, H.; Fukuyama, T. Synlett 2002, 231; (b)
Okano, K.; Tokuyama, H.; Fukuyama, T. Org. Lett. 2003, 5, 4987; (c) Yamada, K.;
Kurokawa, T.; Tokuyama, H.; Fukuyama, T. J. Am. Chem. Soc. 2003, 125, 6630; (d)