Thermoregulated Copper-Free Sonogashira Coupling in Water
[3]
U. Létinois-Halbes, P. Pale, S. Berger, J. Org. Chem. 2005, 70,
9185–9190.
1-(5-Chloropentynyl)-4-nitrobenzene: 108.6 mg (97% yield); yellow
liquid. 1H NMR (400 MHz, CDCl3, TMS): δ = 8.16 (d, J = 8.4 Hz,
2 H, Ar-H), 7.52 (d, J = 8.8 Hz, 2 H, Ar-H), 3.71 (t, J = 6.4 Hz, 2
H, CH2), 2.67 (t, J = 6.8 Hz, 2 H, CH2), 2.06–2.12 (m, 2 H,
CH2) ppm. 13C NMR: δ = 146.89 (Car), 132.45 (2ϫCar), 130.73
(Car), 123.63 (2ϫCar), 94.40 (CϵC), 80.20 (CϵC), 43.70 (CH2),
31.19 (CH2), 17.12 (CH2) ppm. MS (EI): m/z (%) = 223 (100) [M+],
223, 193, 188, 157, 142, 102, 88, 77, 63, 51, 39.
[4]
[5]
B. Panda, T. K. Sarkar, Tetrahedron Lett. 2010, 51, 301–305.
a) K. W. Anderson, S. L. Buchwald, Angew. Chem. Int. Ed.
2005, 44, 6173–6177; b) F. Li, T. S. A. Hor, Adv. Synth. Catal.
2008, 350, 2391–2400; c) A. John, M. M. Shaikh, P. Ghosh,
Dalton Trans. 2009, 10581–10591.
a) C.-J. Li, Chem. Rev. 2005, 105, 3095–3166; b) S. Roy, H.
Plenio, Adv. Synth. Catal. 2010, 352, 1014–1022; c) J. D. Senra,
L. F. B. Malta, M. E. H. M. da Costa, R. C. Michel, L. C. S.
Aguiar, A. B. C. Simas, O. A. C. Antunes, Adv. Synth. Catal.
2009, 351, 2411–2422; d) B. Soberats, L. Martínez, M. Vega,
C. Rotger, A. Costa, Adv. Synth. Catal. 2009, 351, 1727–1731;
e) H. Firouzabadi, N. Iranpoor, M. Gholinejad, J. Mol. Catal.
A: Chem. 2010, 321, 110–116; f) M. Bakherad, A. Keivanloo,
Z. Kalantar, S. Jajarmi, Tetrahedron Lett. 2011, 52, 228–230;
g) D. Rosario-Amorin, M. Gaboyard, R. Clérac, S. Nlate, K.
Heuzé, Dalton Trans. 2011, 40, 44–46.
a) Y. Liang, Y.-X. Xie, J.-H. Li, J. Org. Chem. 2006, 71, 379–
381; b) D. A. Fulmer, W. C. Shearouse, S. T. Medonza, J.
Mack, Green Chem. 2009, 11, 1821–1825; c) A. Carpita, A.
Ribecai, Tetrahedron Lett. 2009, 50, 204–207; d) R. Luque,
D. J. Macquarrie, Org. Biomol. Chem. 2009, 7, 1627–1632; e)
M. Bakherad, A. Keivanloo, B. Bahramian, S. Jajarmi, Appl.
Catal. A 2010, 390, 135–140; f) R. Thorwirth, A. Stolle, B.
Ondruschka, Green Chem. 2010, 12, 985–991.
a) Y. Liu, S.-S. Wang, W. Liu, Q.-X. Wan, H.-Y. Wu, G.-H.
Gao, Curr. Org. Chem. 2009, 13, 1322–1346; b) R. Singh, M.
Sharma, R. Mamgain, D. S. Rawat, J. Braz. Chem. Soc. 2008,
19, 357–379; c) H. Gao, L. McNamee, H. Alper, Org. Lett.
2008, 10, 5281–5284; d) P. G. de Lima, O. A. C. Antunes, Tetra-
hedron Lett. 2008, 49, 2506–2509; e) J. R. Harjani, T. J. Abra-
ham, A. T. Gomez, M. T. Garcia, R. D. Singer, P. J. Scammells,
Green Chem. 2010, 12, 650–655; f) V. Singh, R. Ratti, S. Kaur,
J. Mol. Catal. A: Chem. 2011, 334, 13–19.
[6]
1-(Phenylethynyl)-4-(4-propylcyclohexyl)benzene: 112.4 mg (74%
yield); light-yellow solid (m.p. 87–88 °C). 1H NMR (400 MHz,
CDCl3, TMS): δ = 7.53–7.51 (m, 2 H, Ar-H), 7.45 (dd, J = 8.4,
1.6 Hz, 2 H, Ar-H), 7.35–7.31 (m, 3 H, Ar-H), 7.19 (d, J = 8.4 Hz,
2 H, Ar-H), 2.50–2.43 (m, 1 H, cHex-H), 1.90–1.85 (m, 4 H,
CH2CH2), 1.49–0.99 (m, 9 H, cHex-H), 0.90 (t, J = 8.0 Hz, 3 H,
CH3) ppm. 13C NMR: δ = 148.35 (Car), 131.58 (3ϫCar), 128.32
(2ϫCar), 128.06 (Car), 126.92 (2ϫCar), 123.55 (Car), 120.57 (Car),
89.65 (CϵC), 88.69 (CϵC), 44.60 (CcHex), 39.72 (CcHex), 37.01
(CH2), 34.17 (2ϫCcHex), 33.50 (2ϫCcHex), 20.06 (CH2), 14.45
(CH3) ppm. MS (EI): m/z (%) = 302 (100) [M+], 302, 217, 204, 191,
165, 115, 91, 55.
[7]
[8]
3-{[4-(4-Propylcyclohexyl)phenyl]ethynyl}aniline: 131.8 mg (83%
1
yield); brown solid (m.p. 95–96 °C). H NMR (400 MHz, CDCl3,
TMS): δ = 7.43 (d, J = 8.0 Hz, 2 H, Ar-H), 7.18 (d, J = 8.0 Hz, 2
H, Ar-H), 7.12 (t, J = 8.0 Hz, 1 H, Ar-H), 6.93 (d, J = 8.0 Hz, 1
H, Ar-H), 6.84 (s, 1 H, Ar-H), 6.66–6.63 (m, 1 H, Ar-H), 3.67 (s,
2 H, NH2), 2.47–2.43 (m, 1 H, cHex-H), 1.90–1.85 (m, 4 H,
CH2CH2), 1.49–0.99 (m, 9 H, cHex-H), 0.90 (t, J = 8.0 Hz, 3 H,
CH3) ppm. 13C NMR: δ = 148.24 (Car), 146.24 (Car), 131.56
(2ϫCar), 129.25 (Car), 126.88 (2ϫCar), 124.22 (Car), 122.07 (Car),
120.65 (Car), 117.82 (Car), 115.17 (Car), 89.04 (CϵC), 88.90 (CϵC),
44.59 (CcHex), 39.70 (CcHex), 37.00 (CH2), 34.15 (2ϫCcHex), 33.50
(2ϫCcHex), 20.04 (CH2), 14.42 (CH3) ppm. MS (EI): m/z (%) = 317 [9]
Y. Akiyama, X. Meng, S. Fujita, Y.-C. Chen, N. Lu, H. Cheng,
F. Zhao, M. Arai, J. Supercrit. Fluids 2009, 51, 209–216.
(100) [M+], 317, 232, 206, 193, 165, 97, 55.
[10]
a) C. Wolf, R. Lerebours, Org. Biomol. Chem. 2004, 2, 2161–
2164; b) B. H. Lipshutz, D. W. Chung, B. Rich, Org. Lett. 2008,
10, 3793–3796; c) M. Bakherad, A. Keivanloo, B. Bahramian,
M. Hashemi, Tetrahedron Lett. 2009, 50, 1557–1559; d) M.-J.
Jin, D.-H. Lee, Angew. Chem. Int. Ed. 2010, 49, 1119–1122.
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, characterization data, and copies of
1
the H and 13C NMR spectra of all cross-coupling products.
[11]
[12]
[13]
a) C. A. Fleckenstein, H. Plenio, Chem. Eur. J. 2007, 13, 2701–
2716; b) S. Mori, T. Yanase, S. Aoyagi, Y. Monguchi, T. Mae-
gawa, H. Sajiki, Chem. Eur. J. 2008, 14, 6994–6999; c) R. J.
Brea, M. P. López-Deber, L. Castedo, J. R. Granja, J. Org.
Chem. 2006, 71, 7870–7873.
a) P. Appukkuttan, E. Van der Eycken, Eur. J. Org. Chem.
2003, 4713–4716; b) J. Gil-Moltó, C. Nájera, Eur. J. Org. Chem.
2005, 4073–4081; c) K. M. Dawood, W. Solodenko, A.
Kirschning, ARKIVOC 2007, 5, 104–124; d) G. Chen, X. Zhu,
J. Cai, Y. Wan, Synth. Commun. 2007, 37, 1355–1361.
Acknowledgments
The authors thank the National Natural Science Foundation of
China (NSFC) (grant numbers 20976024, 20923006, 21076034),
Fundamental Research Funds for the Central Universities (grant
number DUT11LK15), Dalian University of Technology (grant
numbers DUTTX2009102, JG0916), and the Ministry of Educa-
tion (Program for New Century Excellent Talents in University) for
financial support.
H. Kawanami, K. Matsushima, M. Sato, Y. Ikushima, Angew.
Chem. Int. Ed. 2007, 46, 5129–5132.
[14]
[15]
M. Osawa, H. Nagai, M. Akita, Dalton Trans. 2007, 827–829.
M. Lamblin, L. Nassar-Hardy, J.-C. Hierso, E. Fouquet, F.-X.
Felpin, Adv. Synth. Catal. 2010, 352, 33–79.
[1] a) K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett.
1975, 16, 4467–4470; b) K. Sonogashira, J. Organomet. Chem.
2002, 653, 46–49; c) E.-I. Negishi, L. Anastasia, Chem. Rev.
2003, 103, 1979–2017; d) R. Chinchilla, C. Nájera, Chem. Rev.
2007, 107, 874–922; e) H. Doucet, J.-C. Hierso, Angew. Chem.
Int. Ed. 2007, 46, 834–871; f) H. Plenio, Angew. Chem. Int. Ed.
2008, 47, 6954–6956.
[2] a) P. Appukkuttan, E. Van der Eycken, Eur. J. Org. Chem.
2008, 1133–1155; b) J. H. Cho, C. D. Prickett, K. H. Shaugh-
nessy, Eur. J. Org. Chem. 2010, 3678–3683; c) I. Malik, Z.
Ahmed, S. Reimann, I. Ali, A. Villinger, P. Langer, Eur. J. Org.
Chem. 2011, 11, 2088–2093; d) B. de Carné-Carnavalet, A. Ar-
chambeau, C. Meyer, J. Cossy, B. Folléas, J.-L. Brayer, J.-P. De-
moute, Org. Lett. 2011, 13, 956–959.
[16]
a) D. E. Bergbreiter, Chem. Rev. 2002, 102, 3345–3384; b) D. E.
Bergbreiter, S. D. Sung, Adv. Synth. Catal. 2006, 348, 1352–
1366; c) A. Corma, H. García, A. Leyva, J. Catal. 2006, 240,
87–99; d) H. Azoui, K. Baczko, S. Cassel, C. Larpent, Green
Chem. 2008, 10, 1197–1203; e) Y. Wang, J. Zhang, W. Zhang,
M. Zhang, J. Org. Chem. 2009, 74, 1923–1931; f) A. Behr, L.
Johnen, N. Rentmeister, Adv. Synth. Catal. 2010, 352, 2062–
2072; g) T. Terashima, M. Ouchi, T. Ando, M. Sawamoto, J.
Polym. Sci., Part A: Polym. Chem. 2010, 48, 373–379; h) K. Li,
Y. Wang, J. Jiang, Z. Jin, Catal. Commun. 2010, 11, 542–546.
[17]
D. E. Bergbreiter, P. L. Osburn, A. Wilson, E. M. Sink, J. Am.
Chem. Soc. 2000, 122, 9058–9064.
Eur. J. Org. Chem. 2011, 4422–4428
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www.eurjoc.org
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