Ruthenium-Catalyzed Cycloisomerization of Aromatic Homo- and Bis-Homopropargylic Amines/Amides
rizi, Chem. Rev. 2005, 105, 2873–2920; c) G. R. Hum-
phrey, J. T. Kuethe, Chem. Rev. 2006, 106, 2875–2911;
d) G. Zeni, R. C. Larock, Chem. Rev. 2006, 106, 4644–
4680; e) N. T. Patil, Y. Yamamoto, Chem. Rev. 2008,
108, 3395–3442.
122, 4374–4377; Angew. Chem. Int. Ed. 2010, 49, 4278–
4281.
[9] THF is the solvent used by Grotjahn for the reaction of
1a (run in NMR tube) to indole 2a, see ref.[7]
[10] a) M. Tokunaga, Y. Wakatsuki, Angew. Chem. 1998,
110, 3024–3027; Angew. Chem. Int. Ed. 1998, 37, 2867–
2869; b) T. Suzuki, M. Tokunaga, Y. Wakatsuki, Org.
Lett. 2001, 3, 735–737; c) M. Tokunaga, T. Suzuki, N.
Koga, T. Fukushima, A. Horiuchi, Y. Wakatsuki, J. Am.
Chem. Soc. 2001, 123, 11917–11924.
[11] Solvent (DMF) and base (NaHCO3) were used for cy-
cloisomerization of bis-homopropargylic alcohols. See
ref.[6]
[12] trans-1-Ethynyl-2-N-tosylaminocyclohexane, an aliphat-
ic acetylene, is recovered unchanged after 24 h under
typical reaction conditions.
[13] a) Secondary N-(methyl)- and N-(phenyl)benzylamines
also failed to undergo heterocyclization, giving complex
mixtures of products. b) For intermolecular anti-Mar-
kovnikov addition of primary and secondary amines to
terminal alkynes, see: Y. Fukumoto, H. Asai, M. Shimi-
zu, N. Chatani, J. Am. Chem. Soc. 2007, 129, 13792–
13793.
[14] This result contrasts with the parent benzylic alcohol
which, using the same Ru catalyst, undergoes 6-endo
cyclization to isochromene in 86% yield (in n-BuNH2)
and 40–62% yield (in pyridine). See ref.[8a]
[15] For intermolecular Ru-catalyzed anti-Markovnikov ad-
dition of amides to alkynes, see: L. J. Gooßen, J. E.
Rauhaus, G. Deng, Angew. Chem. 2005, 117, 4110–
4113; Angew. Chem. Int. Ed. 2005, 44, 4042–4045.
[3] Indoles: a) J. Ezquerra, C. Pedregal, C. Lamas, J. Bar-
luenga, M. PØrez, M. A. García-Martín, J. M. Gonzꢀlez,
J. Org. Chem. 1996, 61, 5804–5812; b) A. Takeda, S.
Kamijo, Y. Yamamoto, J. Am. Chem. Soc. 2000, 122,
5662–5663; c) K. Hiroya, S. Itoh, T. Sakamoto, J. Org.
Chem. 2004, 69, 1126–1136; d) X. Li, A. R. Chianese,
T. Vogel, R. H. Crabtree, Org. Lett. 2005, 7, 5437–
5440; e) T. Kurisaki, T. Naniwa, H. Yamamoto, H.
Imagawa, M. Nishizawa, Tetrahedron Lett. 2007, 48,
1871–1874; f) V. Terrasson, J. Michaux, A. Gaucher, J.
Wehbe, S. Marque, D. Prim, J.-M. Campagne, Eur. J.
Org. Chem. 2007, 2007, 5332–5335; g) Y. Yin, W. Ma,
Z. Chai, G. Zhao, J. Org. Chem. 2007, 72, 5731–5736;
h) Y. Zhang, J. P. Donahue, C.-J. Li, Org. Lett. 2007, 9,
627–630; i) N. Sakai, K. Annaka, A. Fujita, A. Sato, T.
Konakahara, J. Org. Chem. 2008, 73, 4160–4165;
j) G. K. B. Clentsmith, L. D. Field, B. A. Messerle, A.
Shasha, P. Turner, Tetrahedron Lett. 2009, 50, 1469–
1471; k) N. Isono, M. Lautens, Org. Lett. 2009, 11,
1329–1331; l) S. Mehta, J. P. Waldo, R. C. Larock, J.
Org. Chem. 2009, 74, 1141–1147; m) I. Nakamura, Y.
Sato, S. Konta, M. Terada, Tetrahedron Lett. 2009, 50,
2075–2077; n) A. Gimeno, M. Medio-Simón, C. Ramír-
ez de Arellano, G. Asensio, A. B. Cuenca, Org. Lett.
2010, 12, 1900–1903. Isoquinolines: o) Q. Huang, R. C.
Larock, J. Org. Chem. 2003, 68, 980–988; p) N. Asao,
S. Yudha S. , T. Nogami, Y. Yamamoto, Angew. Chem.
2005, 117, 5662–5664; Angew. Chem. Int. Ed. 2005, 44,
5526–5528; q) Q. Ding, J. Wu, Org. Lett. 2007, 9, 4959–
4962; r) K. Gao, J. Wu, J. Org. Chem. 2007, 72, 8611–
8613; s) S. Su, J. A. Porco, Org. Lett. 2007, 9, 4983–
4986; t) D. Fischer, H. Tomeba, N. K. Pahadi, N. T.
Patil, Z. Huo, Y. Yamamoto, J. Am. Chem. Soc. 2008,
130, 15720–15725. Quinolines: u) Z.-Y. Han, H. Xiao,
X.-H. Chen, L.-Z. Gong, J. Am. Chem. Soc. 2009, 131,
9182–9183; v) Z. Huo, I. D. Gridnev, Y. Yamamoto, J.
Org. Chem. 2010, 75, 1266–1270.
[16] a) 11b-Hydroxysteroid dehydrogenase
1
inhibitors:
S. H. Kim, R. Ramu, S. W. Kwon, S.-H. Lee, C. H. Kim,
S. K. Kang, S. D. Rhee, M. A. Bae, S. H. Ahn, D. C.
Ha, H. G. Cheon, K. Y. Kim, J. H. Ahn, Bioorg. Med.
Chem. Lett. 2010, 20, 1065–1069. b) Inhibitors of cyclo-
oxygenase II: H. Blaschke, M. Hartmann, P. Krem-
minger, F. Rovenszky, H. Fellier, J. Berg, T. Christoph,
D. Stimmeder, Ger. Offen. DE 19533643, 1997. c) Sero-
tonin-2-receptor antagonists: A. Mizuno, M. Shibata, T.
Iwamori, N. Inomata, Eur. Pat. Appl. EP 749967A1,
1996.
[17] For the sake of comparison, other conditions were also
[4] For reviews of metal vinylidenes in catalysis, see:
a) M. I. Bruce, Chem. Rev. 1991, 91, 197–257; b) C.
Bruneau, P. H. Dixneuf, Acc. Chem. Res. 1999, 32, 311–
323; c) B. M. Trost, Acc. Chem. Res. 2002, 35, 695–705;
d) C. Bruneau, P. H. Dixneuf, Angew. Chem. 2006, 118,
2232–2260; Angew. Chem. Int. Ed. 2006, 45, 2176–
2203; e) B. M. Trost, A. McClory, Chem. Asian J. 2008,
3, 164–194.
tried: a) 2% [RuCl2ACHTNUTRGNE(UGN p-cymene)]2, 6% PBu3, toluene,
1008C, 3 h, 87% (Goobenꢂs conditions, ref.[15]); b) 2%
RuCl3·H2O, 6% PBu3, toluene 1008C, 60%.
[18] By contrast, the same compounds underwent 5-exo cyc-
lization using TBAF: K. Hiroya, R. Jouka, M. Kameda,
A. Yasuhara, T. Sakamoto, Tetrahedron 2001, 57, 9697–
9710.
[19] a) Substituted 2-(2-propynyl)anilines were efficiently
cyclized using gold catalysts. However, this cyclization
could not be performed with 2-(2-propynyl)aniline to
2H-1,4-dihydroquinoline. See ref.[3u] b) Ru-catalyzed re-
action of parent 2-(2-propynyl)aniline gave decomposi-
tion.
[20] a) D. Touchard, P. Haquette, N. Pirio, L. Toupet, P. H.
Dixneuf, Organometallics 1993, 12, 3132–3139; b) E.
Bustelo, J. J. Carbo, A. Lledós, K. Mereiter, M. C.
Puerta, P. Valerga, J. Am. Chem. Soc. 2003, 125, 3311–
3321; c) Y. Wakatsuki, J. Organomet. Chem. 2004, 689,
4092–4109.
[5] F. E. McDonald, A. K. Chatterjee, Tetrahedron Lett.
1997, 38, 7687–7690.
[6] B. M. Trost, A. McClory, Angew. Chem. 2007, 119,
2120–2123; Angew. Chem. Int. Ed. 2007, 46, 2074–
2077.
[7] R. N. Nair, P. J. Lee, A. L. Rheingold, D. B. Grotjahn,
Chem. Eur. J. 2010, 16, 7992–7995.
[8] a) A. Varela-Fernꢀndez, C. Gonzꢀlez-Rodríguez, J. A.
Varela, L. Castedo, C. Saꢀ, Org. Lett. 2009, 11, 5350–
5353; b) A. Varela-Fernꢀndez, C. García-Yebra, J. A.
Varela, M. A. Esteruelas, C. Saꢀ, Angew. Chem. 2010,
Adv. Synth. Catal. 2011, 353, 1933 – 1937
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1937