Copper-Catalyzed N-Arylation/Hydroamin(d)ation Domino Synthesis of Indoles
FULL PAPERS
McClory, Angew. Chem. 2007, 119, 2120–2123; Angew.
Chem. Int. Ed. 2007, 46, 2074–2077; h) M. McLaughlin,
M. Palucki, I. W. Davies, Org. Lett. 2006, 8, 3307–3310;
i) A. Fꢀrstner, P. W. Davies, J. Am. Chem. Soc. 2005,
127, 15024–15025; j) A. L. Odom, Dalton Trans. 2005,
225–233; k) M. C. Willis, G. N. Brace, I. P. Holmes,
Angew. Chem. 2005, 117, 407–410; Angew. Chem. Int.
Ed. 2005, 44, 403–406; l) T. Shimada, I. Nakamura, Y.
Yamamoto, J. Am. Chem. Soc. 2004, 126, 10546–10547;
m) H. Siebeneicher, I. Bytschkov, S. Doye, Angew.
Chem. 2003, 115, 3151–3153; Angew. Chem. Int. Ed.
2003, 42, 3042–3044; n) M. A. Campo, Y. Huang, T.
Yao, Q. Tian, R. C. Larock, J. Am. Chem. Soc. 2003,
125, 11506–11507, and references cited therein.
[14] T. E. Mueller, K. C. Hultzsch, M. Yus, F. Foubelo, M.
Tada, Chem. Rev. 2008, 108, 3795–3892.
[25] A recent example from our laboratories: L. Acker-
mann, A. Althammer, Angew. Chem. 2007, 119, 1652–
1654; Angew. Chem. Int. Ed. 2007, 46, 1627–1629.
[26] L. Ackermann, Org. Lett. 2005, 7, 439–442.
[27] L. T. Kaspar, L. Ackermann, Tetrahedron 2005, 61,
11311–11316.
[28] For applications of this methodology, see: a) P.-Y. Yao,
Y. Zhang, R. P. Hsung, K. Zhao, Org. Lett. 2008, 10,
4275–4278; b) R. Sanz, M. P. Castroviejo, V. Guilarte,
A. Perez, F. J. Fananas, J. Org. Chem. 2007, 72, 5113–
5118; c) Z.-Y. Tang, Q.-S. Hu, Adv. Synth. Catal. 2006,
348, 846–850.
[29] D. Ma, Q. Cai, Acc. Chem. Res. 2008, 41, 1450–1460.
[30] S. V. Ley, A. W. Thomas, Angew. Chem. 2003, 115,
5558–5607; Angew. Chem. Int. Ed. 2003, 42, 5400–
5449.
[31] K. Kunz, U. Scholz, Synlett 2003, 2428–2439.
[32] For representative recent examples of copper-catalyzed
heteroarene syntheses, see: a) R. C. Hodgkinson, J.
Schulz, M. C. Willis, Org. Biomol. Chem. 2009, DOI:
10.1039/b817254d; b) R. D. Viirre, G. Evindar, R. A.
Batey, J. Org. Chem. 2008, 73, 3452–3459; c) A. Minat-
ti, S. L. Buchwald, Org. Lett. 2008, 10, 2721–2724;
d) R. Martꢄn, A. Cuenca, S. L. Buchwald, Org. Lett.
2007, 9, 5521–5524; e) Y. Chen, X. Xie, D. Ma, J. Org.
Chem. 2007, 72, 9329–9334; f) J. Yuen, Y.-Q. Fang, M.
Lautens, Org. Lett. 2006, 8, 653–656; g) C.-y. Chen,
P. G. Dormer, J. Org. Chem. 2005, 70, 6964–6967, and
references cited therein.
[33] For a related elegant copper-catalyzed domino synthe-
sis of substituted pyrroles and pyrazoles, see: R.
Martꢄn, M. R. Rivero, S. L. Buchwald, Angew. Chem.
2006, 118, 7237–7240; Angew. Chem. Int. Ed. 2006, 45,
7079–7082.
[34] A. A. Kelkar, N. M. Patil, R. V. Chaudhari, Tetrahedron
Lett. 2002, 43, 7143–7146.
[15] R. A. Widenhoefer, Chem. Eur. J. 2008, 14, 5382–5391.
[16] K. C. Hultzsch, Adv. Synth. Catal. 2005, 347, 367–391.
[17] M. Beller, J. Seayad, A. Tillack, H. Jiao, Angew. Chem.
2004, 116, 3448–3479; Angew. Chem. Int. Ed. 2004, 43,
3368–3398.
[18] F. Alonso, I. P. Beletskaya, M. Yus, Chem. Rev. 2004,
104, 3079–3159.
[19] For representative examples of hydroamination reac-
tions from our laboratories, see: a) L. Ackermann, A.
Althammer, Synlett 2008, 995–998; b) L. Ackermann,
L. T. Kaspar, J. Org. Chem. 2007, 72, 6149–6153; c) L.
Ackermann, L. T. Kaspar, A. Althammer, Org. Biomol.
Chem. 2007, 5, 1975–1978; d) L. Ackermann, Organo-
metallics 2003, 22, 4367–4368.
[20] G. Zeni, R. C. Larock, Chem. Rev. 2004, 104, 2285–
2309.
[21] Selected hydroamination-based indole syntheses from
our laboratories: a) L. Ackermann, R. Sandmann, A.
Villar, L. T. Kaspar, Tetrahedron 2008, 64, 769–777;
b) L. Ackermann, A. Althammer, Synlett 2006, 3125–
3129; c) L. Ackermann, L. T. Kaspar, C. J. Gschrei,
Chem. Commun. 2004, 2824–2825; d) L. Ackermann,
R. Born, Tetrahedron Lett. 2004, 45, 9541–9544.
[22] For early examples of copper-mediated reactions, see:
a) C. E. Castro, R. D. Stephens, J. Org. Chem. 1963, 28,
2163; b) C. E. Castro, E. J. Gaughan, D. C. Owsley, J.
Org. Chem. 1966, 31, 4071–4078; for early examples of
catalytic transformations, see: c) K. Utimoto, H. Miwa,
H. Nozaki, Tetrahedron Lett. 1981, 22, 4277–4278;
d) K. Irtani, S. Matsubara, K. Utimoto, Tetrahedron
Lett. 1988, 29, 1799–1802; e) A. Arcadi, S. Cacchi, F.
Marinelli, Tetrahedron Lett. 1989, 30, 2581–2584; f) S.
Cacchi, V. Carnicelli, F. Marinelli, J. Organomet. Chem.
1994, 475, 289–296.
[23] For selected reviews on palladium-catalyzed domino or
cascade coupling reactions, see, for example: a) P. von
Zezschwitz, A. de Meijere, Top. Organomet. Chem.
2006, 19, 49–89; b) A. de Meijere, P. von Zezschwitz, S.
Braese, Acc. Chem. Res. 2005, 38, 413–422; c) A. de
Meijere, P. von Zezschwitz, H. Nuske, B. Stulgies, J. Or-
ganomet. Chem. 2002, 653, 129–140.
[24] L. F. Tietze, G. Brasche, K. M. Gericke, Domino Reac-
tions in Organic Synthesis, Wiley-VCH, Weinheim,
2006.
[35] B. Schlummer, U. Scholz, in: Modern Arylation Meth-
ods, (Ed.: L. Ackermann), Wiley-VCH, Weinheim,
2009, pp 69–120.
[36] D. S. Surry, S. L. Buchwald, Angew. Chem. 2008, 120,
6438–6461; Angew. Chem. Int. Ed. 2008, 47, 6338–
6361.
[37] S. P. Nolan, N-Heterocyclic Carbenes in Synthesis,
Wiley-VCH, Weinheim, 2006.
[38] W. A. Herrmann, Angew. Chem. 2002, 114, 1342–1363;
Angew. Chem. Int. Ed. 2002, 41, 1290–1309.
[39] D. Ma, Y. Zhang, J. Yao, S. Wu, F. Tao, J. Am. Chem.
Soc. 1998, 120, 12459–12467.
[40] J. Folkman, Nature Med. 1995, 1, 27–31.
[41] J. Folkman, N. Engl. J. Med. 1995, 333, 1757–1763.
[42] P. Traxler, Expert Opin. Ther. Targets 2003, 7, 215–234.
[43] G. D. Yancopoulos, S. Davis, N. W. Gale, J. S. Rudge,
S. J. Wiegand, J. Holash, Nature 2000, 407, 242–248.
[44] P. Carmeliet, R. K. Jain, Nature 2000, 407, 249–257.
[45] T. Veikkola, M. Karkkainen, L. Claesson-Welsh, K.
Alitalo, Cancer Res. 2000, 60, 203–212.
[46] K. A. Thomas, J. Biol. Chem. 1996, 271, 603–606.
[47] J. T. Kuethe, A. Wong, I. W. Davies, Org. Lett. 2003, 5,
3975–3978.
[48] M. E. Fraley, K. L. Arrington, C. A. Buser, P. A.
Ciecko, K. E. Coll, C. Fernandes, G. D. Hartman, W. F.
Hoffman, J. J. Lynch, R. C. McFall, K. Rickert, R.
Adv. Synth. Catal. 2009, 351, 1064 – 1072
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