PAPER
Transition-Metal-Catalyzed Synthesis of 1,3-Diynes and Ynamides
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1H NMR (400 MHz, CDCl3): δ = 7.54–7.57 (m, 2 H), 7.40–7.45 (m,
4 H), 7.29–7.31 (m, 4 H), 4.36 (q, J = 7.2 Hz, 2 H), 1.39 (t, J = 7.2
Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 154.3, 139.5, 131.2, 128.9, 128.2,
127.7, 126.9, 124.6, 123.0, 83.0, 70.1, 63.7, 14.3.
He, L.-N. Tetrahedron Lett. 2011, 52, 3485. (g) Oishi, T.;
Yamaguchi, K.; Mizuno, N. ACS Catal. 2011, 1, 1351.
(h) Zhang, S.; Liu, X.; Wang, T. Adv. Synth. Catal. 2011,
353, 1463. (i) Wu, T.-M.; Huang, S.-H.; Tsai, F.-Y. Appl.
Organomet. Chem. 2011, 25, 395. (j) Schmidt, R.;
Thorwirth, R.; Szuppa, T.; Stolle, A.; Ondruschka, B.; Hopf,
H. Chem. Eur. J. 2011, 17, 8129. (k) Alonso, F.; Melkonian,
T.; Moglie, Y.; Yus, M. Eur. J. Org. Chem. 2011, 2524.
(l) Kusuda, A.; Xu, X.-H.; Wang, X.; Tokunaga, E.; Shibata,
N. Green Chem. 2011, 13, 843.
MS (EI): m/z = 265, 206, 192, 165, 115, 103, 89, 77, 63, 51.
Anal. Calcd for C17H15NO2: C, 76.96; H, 5.70; N, 5.28. Found: C,
76.72; H, 5.77; N, 5.33.
Ethyl Phenyl[(4-tolyl)ethynyl]carbamate (3k)
Yellow oil; yield: 66 mg (94%).
IR (KBr): 3428, 2253, 1737, 1635, 1279, 1125, 511 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.56–7.58 (m, 2 H), 7.40–7.44 (m,
2 H), 7.35 (d, J = 8.4 Hz, 2 H), 7.27–7.31 (m, 1 H), 7.12 (d, J = 8.0
Hz, 2 H), 4.36 (q, J = 7.2 Hz, 2 H), 2.35 (s, 3 H), 1.39 (t, J = 7.2 Hz,
3 H).
13C NMR (100 MHz, CDCl3): δ = 154.3, 139.7, 137.8, 131.3, 129.0,
128.9, 126.8, 124.6, 119.9, 82.3, 70.1, 63.7, 21.4, 14.4.
(4) (a) Wang, D.; Li, J.; Li, N.; Gao, T.; Hou, S.; Chen, B. Green
Chem. 2010, 12, 45. (b) Li, L.; Wang, J.; Zhang, G.; Liu, Q.
Tetrahedron Lett. 2009, 50, 4033. (c) Yin, W.; He, C.; Chen,
M.; Zhang, H.; Lei, A. Org. Lett. 2009, 11, 709.
(d) Adimurthy, S.; Malakar, C. C.; Beifuss, U. J. Org. Chem.
2009, 74, 5648. (e) Kamata, K.; Yamaguchi, S.; Kotani, M.;
Yamaguchi, K.; Mizuno, N. Angew. Chem. Int. Ed. 2008, 47,
2407. (f) Yamaguchi, K.; Kamata, K.; Yamaguchi, S.;
Kotani, M.; Mizuno, N. J. Catal. 2008, 258, 121. (g) Li, D.;
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U.; Prasad, A. R. Tetrahedron Lett. 2003, 44, 6493. (j) Li, J.;
Jiang, H. Chem. Commun. 1999, 2369.
MS (EI): m/z = 279, 220, 206, 165, 117, 103, 77, 51.
Anal. Calcd for C18H17NO2: C, 77.40; H, 6.13; N, 5.01. Found: C,
77.23; H, 6.18; N, 5.07.
(5) For Pd/Cu-catalyzed homocoupling reactions of terminal
alkynes, see: (a) Chen, S.-N.; Wu, W.-Y.; Tsai, F.-Y. Green
Chem. 2009, 11, 269. (b) Yang, F.; Cui, X.; Li, Y.-n.; Zhang,
J.; Ren, G.; Wu, Y. Tetrahedron 2007, 63, 1963. (c) Yan, J.;
Wu, J.; Jin, H.-x. J. Organomet. Chem. 2007, 692, 3636.
(d) Shi, M.; Qian, H. Appl. Organomet. Chem. 2006, 20,
771. (e) Batsanov, A. S.; Collings, J. C.; Fairlamb, I. J. S.;
Holland, J. P.; Howard, J. A. K.; Lin, Z.; Marder, T. B.;
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703. (f) Li, J.-H.; Liang, Y.; Xie, Y.-X. J. Org. Chem. 2005,
70, 4393. (g) Li, J.-H.; Liang, Y.; Zhang, X.-D. Tetrahedron
2005, 61, 1903. (h) Fairlamb, I. J. S.; Bäuerlein, P. S.;
Marrison, L. R.; Dickinson, J. M. Chem. Commun. 2003,
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(6) For Cu-catalyzed homocoupling reactions of internal
alkynes, see: (a) Paixão, M. W.; Weber, M.; Braga, A. L.; de
Azeredo, J. B.; Deobald, A. M.; Stefani, H. A. Tetrahedron
Lett. 2008, 49, 2366. (b) Nishihara, Y.; Okamoto, M.; Inoue,
Y.; Miyazaki, M.; Miyasaka, M.; Takagi, K. Tetrahedron
Lett. 2005, 46, 8661. (c) Nishihara, Y.; Ikegashira, K.;
Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, Y. J. Org.
Chem. 2000, 65, 1780.
Ethyl [(4-Chlorophenyl)ethynyl]phenylcarbamate (3l)
Yellow oil; yield: 64 mg (85%).
IR (KBr): 3415, 2253, 1738, 1490, 1369, 1277, 1125, 755, 693, 512
cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.52–7.54 (m, 2 H), 7.40–7.43 (m,
2 H), 7.33–7.36 (m, 2 H), 7.26–7.30 (m, 3 H), 4.35 (q, J = 7.2 Hz, 2
H), 1.38 (t, J = 7.2 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 154.1, 139.4, 133.6, 132.4, 129.0,
128.5, 127.1, 124.7, 121.5, 83.9, 69.1, 63.8, 14.3.
MS (EI): m/z = 299, 240, 226, 191, 165, 137, 123, 77, 51.
Anal. Calcd for C17H14ClNO2: C, 68.12; H, 4.71; N, 4.67. Found: C,
67.86; H, 4.79; N, 4.61.
Acknowledgment
This research was supported by the NSFC (21202023 and
21162001), NSF of Jiangxi Provincial Education Department
(GJJ14654).
Supporting Information for this article is available online
at
10.1055/s-00000084.SunpfgIpi
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(7) For Pd-catalyzed homocoupling reactions of internal
alkynes, see: (a) Singh, F. V.; Amaral, M. F. Z. J.; Stefani,
H. A. Tetrahedron Lett. 2009, 50, 2636. (b) Oh, C. H.;
Reddy, V. R. Tetrahedron Lett. 2004, 45, 5221. (c) Yoshida,
H.; Yamaryo, Y.; Ohshita, J.; Kunai, A. Chem. Commun.
2003, 1510. (d) Shirakawa, E.; Nakao, Y.; Murota, Y.;
Hiyama, T. J. Organomet. Chem. 2003, 670, 132.
(8) (a) Shen, W.; Thomas, S. A. Org. Lett. 2000, 2, 2857.
(b) Huang, Z.; Shang, R.; Zhang, Z.-R.; Tan, X.-D.; Xiao,
X.; Fu, Y. J. Org. Chem. 2013, 78, 4551.
(9) For selected reviews, see: (a) DeKorver, K. A.; Li, H.;
Lohse, A. G.; Hayashi, R.; Lu, Z.; Zhang, Y.; Hsung, R. P.
Chem. Rev. 2010, 110, 5064. (b) Evano, G.; Coste, A.;
Jouvin, K. Angew. Chem. Int. Ed. 2010, 49, 2840. (c) Wang,
X.-N.; Yeom, H.-S.; Fang, L.-C.; He, S.; Ma, Z.-X.;
Kedrowski, B. L.; Hsung, R. P. Acc. Chem. Res. 2014, 47,
560.
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