6912
J. Choe et al. / Tetrahedron Letters 53 (2012) 6908–6912
(m, 1H), 5.39 (m, 1H), 5.15 (m, 1H), 3.78 (s, 3H), 3.17 (dt, J = 5.3, 1.8 Hz, 2H); 13
5. (a) Moon, J.; Jang, M.; Lee, S. J. Org. Chem. 2009, 74, 1403–1406; (b) Park, K.; Bae,
G.; Moon, J.; Choe, J.; Song, K. H.; Lee, S. J. Org. Chem. 2010, 75, 6244–6251; (c)
Park, K.; Bae, G.; Park, A.; Kim, Y.; Choe, J.; Song, K. H.; Lee, S. Tetrahedron Lett.
2011, 52, 576–580; (d) Lee, H. J.; Park, K.; Bae, G.; Choe, J.; Song, K. H.; Lee, S.
Tetrahedron Lett. 2011, 52, 5064–5067; (e) Tartaggia, S.; Lucchi, O. D.; Gooben,
L. J. Eur. J. Org. Chem. 2012, 1431–1438; (f) Park, K.; Palani, T.; Pyo, A.; Lee, S.
Tetrahedron Lett. 2012, 53, 733–737.
6. Kim, H.; Lee, P. H. Adv. Synth. Catal. 2009, 351, 2827–2832.
7. Zhang, W.-W.; Zhang, X.-G.; Li, J.-H. J. Org. Chem. 2010, 75, 5259–5264.
8. Zhao, D.; Gao, C.; Su, X.; He, Y.; You, J.; Xue, Y. Chem. Commun. 2010, 46, 9049–
9051.
C
NMR (75 MHz, CDCl3) d 159.1, 132.9, 132.6, 116.0, 115.8, 113.8, 84.9, 82.6, 55.2,
23.7.
1-Chloro-4-(pent-4-en-1-ynyl)benzene (3fa):
1H NMR (300 MHz, CDCl3) d 7.35 (d, J = 8.7 Hz, 2H), 7.26 (d, J = 9.0 Hz, 2H), 5.89
(m, 1H), 5.38 (m, 1H), 5.17 (m, 1H), 3.18 (dt, J = 5.3, 1.8 Hz, 2H); 13C NMR
(75 MHz, CDCl3) d 133.7, 132.8, 132.2, 129.6, 122.2, 116.4, 87.6, 81.8, 23.7.
1-Methyl-3-(pent-4-en-1-ynyl)benzene (3ga):
1H NMR (300 MHz, CDCl3) d 7.28-7.04 (m, 4H), 5.89 (m, 1H), 5.40 (m, 1H), 5.15
(m, 1H), 3.18 (dt, J = 5.3, 1.8 Hz, 2H), 2.30 (s, 3H); 13C NMR (75 MHz, CDCl3) d
137.8, 132.5, 132.2, 128.6, 128.1, 123.5, 116.2, 86.1, 83.0, 23.7, 21.2.
1-Methyl-2-(pent-4-en-1-ynyl)benzene (3ha):
9. Qu, X.; Li, T.; Sun, P.; Zhu, Y.; Yang, H.; Mao, J. Org. Biomol. Chem. 2011, 9, 6938–
6942.
1H NMR (300 MHz, CDCl3) d 7.39 (d, J = 7.2 Hz, 1H), 7.18–7.06 (m, 3H), 5.91 (m,
1H), 5.43 (m, 1H), 5.16 (m, 1H), 3.23 (dt, J = 5.2, 1.8 Hz, 2H), 2.43 (s, 3H); 13C
NMR (75 MHz, CDCl3) d 139.9, 132.6, 131.9, 129.3, 127.7, 125.4, 123.5, 116.1,
90.4, 81.8, 23.8, 20.7;
10. Feng, C.; Loh, T.-P. Chem. Commun. 2010, 46, 4779–4781.
11. (a) Jia, W.; Jiao, N. Org. Lett. 2010, 12, 2000–2003; (b) Hu, J.; Zhao, N.; Yang, B.;
Wang, G.; Guo, L. N.; Liang, Y. M.; Yang, S. D. Chem. Eur. J. 2011, 17, 5516–5521.
12. (a) Kim, Y.; Park, A.; Park, K.; Lee, S. Tetrahedron Lett. 2011, 52, 1766–1769; (b)
Park, J.; Park, E.; Kim, A.; Park, S.-A.; Lee, Y.; Chi, K.-W.; Jung, Y. H.; Kim, I. S. J.
Org. Chem. 2011, 76, 2214–2219.
1-(Pent-4-en-1-ynyl)naphthalene (3ia):
1H NMR (300 MHz, CDCl3) d 8.36 (m, 1H), 7.85-7.32 (m, 6H), 5.97 (m, 1H), 5.50
(m, 1H), 5.21 (m, 1H), 3.33 (dt, J = 5.2, 1.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
133.4, 133.1, 132.5, 130.1, 128.2, 128.1, 126.5, 126.2, 125.2, 121.4, 116.3, 91.5,
80.9, 24.0.
13. Park, A.; Park, K.; Kim, Y.; Lee, S. Org. Lett. 2011, 13, 944–947.
14. Kolarovic, A.; Fáberová, Z. J. Org. Chem. 2009, 74, 7199–7202.
ˇ
15. (a) Feng, H.; Ermolatev, D. S.; Song, G.; van der Eycken, E. V. J. Org. Chem. 2012,
77, 5149–5154; (b) Palani, T.; Park, K.; Kumar, M. R.; Jung, H. M.; Lee, S. Eur. J.
1-(4-(Pent-4-en-1-ynyl)phenyl)ethanone (3ja):
1H NMR (300 MHz, CDCl3) d 7.93–7.84 (m, 2H), 7.54–7.45 (m, 2H), 5.90 (m, 1H),
5.40 (m, 1H), 5.19 (m, 1H), 3.22 (dt, J = 5.3, 1.8 Hz, 2H), 2.59 (s, 3H); 13C NMR
(75 MHz, CDCl3) d 197.4, 135.9, 131.9, 131.7, 128.2, 127.0, 116.6, 90.4, 82.2,
26.6, 23.8.
ˇ
16. Kolarovic, A.; Schnürch, M.; Mihovilovic, M. D. J. Org. Chem. 2011, 76, 2613–
2618.
17. (a) Rayabarapu, D. K.; Tunge, J. A. J. Am. Chem. Soc. 2005, 127, 13510–13511; (b)
Waver, J. D.; Recio, A., III; Grenning, A. J.; Tunge, J. A. Chem. Rev. 2011, 111,
1846–1913.
18. (a) Mignani, G.; Chevalier, C.; Grass, F.; Allmang, G.; Morel, D. Tetrahedron Lett.
1990, 31, 5161–5164; Intramolecular decarboxylative allylation see: (b)
Grushin, V.; Alper, H. J. Org. Chem. 1992, 57, 2188–2192; (c) Bieber, L. W.; da
Silva, M. F. Tetrahedron Lett. 2007, 48, 7088–7090.
19. (a) Catellani, M.; Ghiusoli, G. P.; Salerno, G.; Dallatomasina, F. J. Organomet.
Chem. 1978, 146, 19–22; (b) Cui, D.-M.; Hashimoto, N.; Ikeda, S.-I.; Sato, Y. J.
Org. Chem. 1995, 60, 5752–5756; (c) Leadbeater, N. E. J. Org. Chem. 2001, 66,
7539–7541; (d) Yatsumonji, Y.; Ishida, Y.; Tsubouchi, A.; Takeda, T. Org. Lett.
2007, 9, 4603–4606.
Methyl 4-(pent-4-en-1-ynyl)benzoate (3ka):
1H NMR (300 MHz, CDCl3) d 7.97 (m, 2H), 7.47 (m ,2H), 5.90 (m, 1H), 5.40 (m,
1H), 5.18 (m, 1H), 3.91 (s, 3H), 3.22 (dt, J = 5.3, 1.8 Hz, 2H); 13C NMR (75 MHz,
CDCl3) d 166.6, 131.9, 131.5, 129.4, 129.1, 128.5, 116.5, 90.0, 82.3, 52.2, 23.8.
(E)-Pent-1-en-4-yne-1,5-diyldibenzene (3ac):
1H NMR (300 MHz, CDCl3) d 7.48–7.19 (m, 10H), 6.70 (dt, J = 15.8, 1.8 Hz, 1H),
6.23 (dt, J = 15.7, 5.6 Hz, 1H), 3.35 (dd, J = 5.6, 1.8 Hz, 2H); 13C NMR (75 MHz,
CDCl3) d 137.1, 131.6, 131.4, 128.8, 128.5, 128.2, 127.8, 127.3, 126.2, 124.2,
123.6, 86.7, 82.8, 23.0.
21. The ratio was determined by 1H NMR: (E)-dec-4-en-1-ynylbenzene (3ab-L):1H
NMR (300 MHz, CDCl3) d 7.42 (m, 2H), 7.30–7.25 (m, 3H), 5.75 (m, 1H), 5.50 (m,
1H), 3.13 (ddd, J = 5.5, 2.8, 1.4 Hz, 2H), 2.05 (dq, J = 6.9, 1.0 Hz, 2H), 1.28–1.31
(m, 6H), 0.90 (t, J = 6.8 Hz, 3H); (3-Vinyloct-1-ynyl)benzene (3ab-B): 1H NMR
(300 MHz, CDCl3) d 7.42 (m, 2H), 7.29–7.25 (m, 3H), 5.84 (ddd, J = 16.9, 10.0,
6.1 Hz, 1H), 5.36 (dt, J = 17.0, 1.6 Hz, 1H), 5.11 (dt, 10.0, 1.5 Hz, 1H), 3.27 (q,
J = 6.7 Hz, 1H), 1.46 (m, 2H), 1.32–1.23 (m, 6H), 0.88 (t, J = 6.8 Hz, 3H).
22. (a) Hashmi, A. S. K. In Modern Allene Chemistry; Krause, N., Hashmi, A. S. K., Eds.;
Weinhelim: Wiley-VCH Verlag, 2004; Vol. 1, pp 3–36; 2 Ma, S. In Modern Allene
Chemistry; Krause, N., Hashmi, A. S. K., Eds.; Wiley-VCH Verlag: Weinhelm,
2004; Vol. 2, pp 595–684; (c) Wei, L.-L.; Xiong, H.; Hsung, R. P. Acc. Chem. Res.
2003, 36, 773; (d) Kim, H.; Williams, L. J. Curr. Opin. Drug Discovery Dev. 2008,
11, 870.
20. Typical experimental procedure: Ni(OAc)2ꢀ4H2O (74.6 mg, 0.3 mmol), 1,4-
bis(diphenylphosphino)butane (153.5 mg, 0.36 mmol), aryl alkynyl carboxylic
acids (3.0 mmol), allyl acetate (6.0 mmol), AgOAc (50.1 mg, 0.3 mmol), and
zinc (196.2 mg, 3.0 mmol) were combined with DMSO (10 mL) in a small
round-bottomed flask. The resulting mixture was stirred at 100 °C for 0.5 h.
The reaction mixture was poured into water and extracted with EtOAc. The
solvent was removed under vacuum, and the resulting crude product was
purified by flash chromatography on silica gel to give the desired product.
Pent-4-en-1-ynylbenzene (3aa):
1H NMR (300 MHz, CDCl3) d 7.46–7.22 (m, 5H), 5.89 (m, 1H), 5.40 (m, 1H), 5.16
(m, 1H), 3.18 (dt, J = 5.3 1.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) d 132.4, 131.5,
128.2, 127.7, 123.7, 116.2, 86.5, 82.8, 23.7.
23. Ruitenberg, K.; Kleijn, H.; Elsevier, C. J.; Meijer, J.; Vermeer, P. Tetrahedron Lett.
1981, 22, 1451–1452.
1-Methyl-4-(pent-4-en-1-ynyl)benzene (3ba):
24. Typical experimental procedure: Ni(OAc)2ꢀ4H2O (74.6 mg, 0.3 mmol), 1,4-
bis(diphenylphosphino)butane (153.5 mg, 0.36 mmol), aryl alkynyl carboxylic
acids (3.0 mmol), allyl acetate (6.0 mmol), AgOAc (50.1 mg, 0.3 mmol), zinc
(196.2 mg, 3.0 mmol), and DBU (456.7 mg, 3.0 mmol) were combined with
DMSO (10 mL) in a small round-bottomed flask. The resulting mixture was
stirred at 100 °C for 2 h. The reaction mixture was poured into water and
extracted with EtOAc. The solvent was removed under vacuum, and the
resulting crude product was purified by flash chromatography on silica gel to
give the desired product.
1H NMR (300 MHz, CDCl3) d 7.31 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 7.8 Hz, 2H), 5.89
(m, 1H), 5.40 (m, 1H), 5.15 (m, 1H), 3.18 (dt, J = 5.3, 1.8 Hz, 2H), 2.33 (s, 3H); 13
NMR (75 MHz, CDCl3) d 137.7, 132.6, 131.4, 128.9, 120.6, 116.1, 85.7, 82.9, 23.7,
21.4.
C
1-Ethyl-4-(pent-4-en-1-ynyl)benzene (3ca):
1H NMR (300 MHz, CDCl3) d 7.34 (d, J = 8.2 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 5.90
(m, 1H), 5.40 (m, 1H), 5.15 (m, 1H), 3.18 (dt, J = 5.2, 1.8 Hz, 2H), 2.64 (q,
J = 7.6 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H); 13C NMR (75 MHz, CDCl3) d 144.0, 132.6,
131.5, 127.7, 120.8, 116.1, 85.7, 82.9, 28.7, 23.7, 16.3.
Penta-1,2,4-trienylbenzene (5a):
1-tert-Butyl-4-(pent-4-en-1-ynyl)benzene (3da):
1H NMR (300 MHz, CDCl3) d 7.35–7.16 (m, 5H), 6.42–6.13 (m, 3H), 5.30 (m, 1H),
5.09 (m, 1H); 13C NMR (75 MHz, CDCl3) d 209.4, 133.8, 132.0, 128.6, 127.1,
126.9, 116.8, 98.3, 95.9.
1H NMR (300 MHz, CDCl3) d 7.36 (d, J = 8.7 Hz, 2H), 7.30 (d, J = 8.7 Hz, 2H), 5.89
(m, 1H), 5.40 (m, 1H), 5.15 (m, 1H), 3.17 (dt, J = 5.2, 1.8 Hz, 2H), 1.29 (s, 9H); 13
C
NMR (75 MHz, CDCl3) d 150.8, 132.6, 131.3, 125.2, 120.7, 116.1, 85.7, 82.9, 34.6,
31.2, 23.7.
1-Methyl-4-(penta-1,2,4-trienyl)benzene (5b):
1H NMR (300 MHz, CDCl3) d 7.21–7.11 (m, 4H), 6.35–6.17 (m, 3H), 5.29 (m,
1H), 5.08 (m, 1H), 2.33 (s, 3H); 13C NMR (75 MHz, CDCl3) d 209.2, 137.0, 132.3,
130.8, 129.4, 126.9, 116.6, 98.2, 95.7, 29.7.
1-Methoxy-4-(pent-4-en-1-ynyl)benzene (3ea):
1H NMR (300 MHz, CDCl3) d 7.36 (d, J = 8.6 Hz, 2H), 6.80 (d, J = 8.9 Hz, 2H), 5.89