PAPER
Solvent- and Ligand-Free Palladium-Catalyzed Amination
3155
Anal. Calcd for C13H11ClN2O2: C, 59.44; H, 4.22; N, 10.66. Found:
C, 59.21; H, 4.39; N, 10.44.
References
(1) (a) Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675.
(b) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.;
Tada, M. Chem. Rev. 2008, 108, 3795. (c) Kienle, M.;
Dubbaka, S. R.; Brade, K.; Knochel, P. Eur. J. Org. Chem.
2007, 4166. (d) Kotov, V.; Scarborough, C. C.; Stahl, S. S.
Inorg. Chem. 2007, 46, 1910. (e) Wolfe, J. P. Eur. J. Org.
Chem. 2007, 571. (f) Minatti, A.; Muniz, K. Chem. Soc. Rev.
2007, 36, 1142. (g) Hesp, K. D.; Stradiotto, M.
(4-Methoxyphenyl)methyl(4-nitrophenyl)amine (4)
Yellow solid; conversion: 67%; yield: 152.1 mg (88%); mp 122–
123 °C (hexane–Et2O).
1H NMR (200 MHz, CDCl3): δ = 3.35 (s, 3 H, N-Me), 3.84 (s, 3 H,
O-Me), 6.58 (d, J = 9.4 Hz, 2 H, Ar p-NO2), 6.97 (d, J = 9.0 Hz, 2
H, Ar p-OMe), 7.13 (d, J = 9.0 Hz, 2 H, Ar p-OMe), 8.04 (d, J = 9.4
Hz, 2 H, Ar p-NO2).
ChemCatChem 2011, 2, 1346.
13C NMR (50 MHz, CDCl3): δ = 40.7, 55.3, 114.8, 127.3, 128.5,
132.3, 138.9, 145.2, 152.8, 154.4.
(2) (a) The Chemistry and Application of Dyes; Waring, D. R.;
Hallas, G., Eds.; Plenum: New York, 1990. (b) Hili, R.;
Yudin, A. K. Nat. Chem. Biol. 2006, 2, 284. (c) D’Aprano,
G.; Leclerc, M.; Zott, G.; Schiavon, G. Chem. Mater. 1995,
7, 33. (d) He, F.; Foxman, B. M.; Snider, B. B. J. Am. Chem.
Soc. 1998, 120, 6417.
(3) (a) Buchwald, S. L.; Mauger, C.; Mignani, G.; Scholz, U.
Adv. Synth. Catal. 2006, 348, 23. (b) Corbet, J. P.; Mignani,
G. Chem. Rev. 2006, 106, 2651. (c) Surry, D. S.; Buchwald,
S. L. Angew. Chem. Int. Ed. 2008, 47, 6338; Angew. Chem.
2008, 120, 6438. (d) Busacca, C. A.; Fandrick, D. R.; Song,
J. J.; Senanayake, C. H. Adv. Synth. Catal. 2011, 353, 1825.
(e) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41,
1461. (f) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37,
2046; Angew. Chem. 1998, 110, 2154.
(4) (a) Guram, A. S.; Rennels, R. A.; Buchwald, S. L. Angew.
Chem. Int. Ed. 1995, 34, 1348; Angew. Chem. 1995, 107,
1456. (b) Louie, J.; Hartwig, J. F. Tetrahedron Lett. 1995,
36, 3609.
(5) Hartwig, J. F. Organotransition Metal Chemistry: From
Bonding to Catalysis; University Science Books: Sausalito,
2010.
Anal. Calcd for C14H14N2O3: C, 65.11; H, 5.46; N, 10.85. Found: C,
65.01; H, 5.60; N, 10.72.
N,4-Dimethyl-N-(4-nitrophenyl)aniline (5)
Yellow solid; conversion: 50%; yield: 99.2 mg (82%); mp 77–
79 °C (hexane–Et2O).
1H NMR (200 MHz, CDCl3): δ = 2.39 (s, 3 H, Me), 3.37 (s, 3 H, N-
Me), 6.63 (d, J = 9.4 Hz, 2 H, Ar p-NO2), 7.10 (d, J = 8.4 Hz, 2 H,
Ar p-Me), 7.26 (d, J = 8.4 Hz, 2 H, Ar p-Me), 8.04 (d, J = 9.4 Hz,
2 H, Ar p-NO2).
13C NMR (50 MHz, CDCl3): δ = 21.3, 40.8, 112.4, 126.0, 126.8,
131.0, 137.0, 138.2, 144.0, 154.2.
Anal. Calcd for C14H14N2O2: C, 69.41; H, 5.82; N, 11.56. Found: C,
69.33; H, 5.94; N, 11.38.
N-Methyl-N-(4-nitrophenyl)pyridin-2-amine (6)20
Dark-yellow solid; conversion: 55%; yield: 112.1 mg (89%); mp
107–109 °C (hexane–Et2O).
1H NMR (200 MHz, CDCl3): δ = 3.54 (s, 3 H, N-Me), 6.94 (dd,
J = 7.3, 5.0 Hz, 1 H, py), 7.06 (d, J = 8.4 Hz, 1 H, py), 7.15 (d,
J = 9.2 Hz, 2 H, Ar p-NO2), 7.59 (ddd, J = 8.4, 7.3, 1.8 Hz, 1 H, py),
8.11 (d, J = 9.2 Hz, 2 H, Ar p-NO2), 8.35 (dd, J = 5.0, 1.8 Hz, 1 H,
py).
(6) (a) Surry, D. S.; Buchwald, S. L. Chem. Sci. 2011, 2, 27.
(b) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534.
(c) Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.;
Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem.
1999, 64, 5575. (d) Watanabe, M.; Nishiyama, M.;
Yamamoto, T.; Koie, Y. Tetrahedron Lett. 2000, 41, 481.
(e) Old, D. W.; Harris, M. C.; Buchwald, S. L. Org. Lett.
2000, 2, 1403. (f) Tardiff, B. J.; McDonald, R.; Ferguson, M.
J.; Stradiotto, M. J. Org. Chem. 2012, 77, 1056. (g) Tardiff,
B. J.; Stradiotto, M. Eur. J. Org. Chem. 2012, 3972.
(h) Chen, L.; Yu, G.-A.; Li, F.; Zhu, X.; Zhang, B.; Guo, R.;
Li, X.; Yang, Q.; Jin, S.; Liu, C.; Liu, S.-H. J. Organomet.
Chem. 2010, 695, 1768.
13C NMR (50 MHz, CDCl3): δ = 38.3, 115.0, 118.5, 119.1, 125.5,
138.1, 141.5, 149.0, 152.7, 157.7.
Anal. Calcd for C12H11N3O2: C, 62.87; H, 4.84; N, 13.96. Found: C,
62.63; H, 4.95; N, 13.83.
1-Pyridin-4-yl-1,2,3,4-tetrahydroquinoline (11)
Yellow oil; conversion: 47%; yield: 81.8 mg (83%).
1H NMR (200 MHz, CDCl3): δ = 2.03 (m, 2 H, CH2), 2.74 (m, 2 H,
CH2-Ar), 3.66 (t, J = 6.2 Hz, 2 H, CH2-N), 7.00 (m, 2 H, Ar), 7.04
(m, 2 H, py), 7.29 (d, J = 7.3 Hz, 2 H, Ar), 8.31 (d, J = 5.5 Hz, 2 H,
py).
(7) For ligand-free Heck reactions, see: (a) Dong, J. J.; Roger,
J.; Pozgan, F.; Doucet, H. Green Chem. 2009, 11, 1832.
(b) de Vries, A. H. M.; Parlevliet, F. J.; Schmieder-van de
Vondervoort, L.; Mommers, J. H. M.; Henderickx, H. J. W.;
Walet, M. A. M.; de Vries, J. G. Adv. Synth. Catal. 2002,
344, 996. (c) Beletskaya, I. P.; Kashin, A. N.; Karlstedt, N.
B.; Mitin, A. V.; Cheprakov, A. V.; Kazankov, G. M.
J. Organomet. Chem. 2001, 622, 89. (d) de Vries, A. H. M.;
Mulders, J. M. C. A.; Mommers, J. H. M.; Henderickx, H. J.
W.; de Vries, J. G. Org. Lett. 2003, 5, 3285. (e) Gruber, A.
S.; Zim, D.; Ebeling, G.; Monteiro, A. L.; Dupont, J. Org.
Lett. 2000, 2, 1287. (f) Alonso, D. A.; Najera, C.; Pacheco,
M. C. Org. Lett. 2000, 2, 1823. (g) Beccalli, E. M.; Borsini,
E.; Brenna, S.; Galli, S.; Rigamonti, M.; Broggini, G. Chem.
Eur. J. 2010, 16, 1670. (h) Sun, P.; Qu, X.; Li, T.; Zhu, Y.;
Yang, H. L.; Xing, Z. Y.; Mao, J. C. Synlett 2012, 23, 150.
(8) For ligand-free arylation reactions, see: (a) Basolo, L.;
Beccalli, E. M.; Borsini, E.; Broggini, G. Tetrahedron 2009,
65, 3486. (b) Bellina, F.; Benelli, F.; Rossi, R. J. Org. Chem.
2008, 73, 5529. (c) Wang, X.; Gribkov, D. V.; Sames, D. J.
J. Org. Chem. 2007, 72, 1476. (d) Roger, J.; Doucet, H. Adv.
Synth. Catal. 2009, 351, 1977. (e) Fu, H.; Chen, L.; Doucet,
13C NMR (50 MHz, CDCl3): δ = 24.1, 27.2, 47.7, 111.8, 121.0,
123.2, 126.4, 129.1, 131.6, 139.9, 148.7, 154.0.
Anal. Calcd for C14H14N2: C, 79.97; H, 6.71; N, 13.32. Found: C,
79.78; H, 6.90; N, 13.13.
Acknowledgment
We acknowledge financial support from MIUR (Prin 2010 prot.
20109Z2XRJ). We are also grateful to the Centro Interuniversitario
di Ricerca sulle Reazioni Pericicliche e Sintesi di Sistemi Etero e
Carbociclici.
Supporting Information for this article is available online at
n
nfomartit
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 3151–3156