´
A. Takacs et al. / Tetrahedron 64 (2008) 9874–9878
9878
4.6.3. Tridec-2-ynoic acid tert-butylamide (7a)
3H, CH3). 13C NMR (CDCl3)
d: 170.6, 166.0, 146.0, 122.7, 52.3, 41.2,
1H NMR (CDCl3)
d
: 5.52 (br s, 1H, NH), 2.21 (t, J¼7.1 Hz, 2H, CH2),
32.0, 31.9, 29.6, 29.5, 29.4, 29.3, 29.1, 28.2, 22.6, 14.1. IR (KBr,
(cmꢁ1)): 3305 (NH), 1745 (COO), 1671 (CON), 1633 (C]C). MS m/z
(rel int. %): 283 (4) (Mþ), 252 (5), 195 (100), 152 (10), 131 (15), 81
(25), 55 (47). Anal. Calcd for C16H29NO3 (283.41): C, 67.81; H, 10.31;
N, 4.94. Found: C, 67.70; H,10.45; N, 4.79. Rf (30% EtOAc/CHCl3) 0.59.
Pale-yellow crystalline material, mp 64–65 ꢀC.
1.50 (br qi, J¼7.1 Hz, 2H, CH2),1.36 (s, 3H, tBu),1.2–1.4 (m,14H, chain
methylenes), 0.84 (t, J¼6.8 Hz, 3H, CH3). 13C NMR (CDCl3)
d: 159.6,
152.7, 85.1, 76.6, 52.0, 31.8, 29.5, 29.4, 29.3, 29.0, 28.9, 28.6, 28.2,
27.8, 22.6, 18.5, 14.0. IR (KBr, (cmꢁ1)): 3329 (NH), 2241 (C^C), 1634
(CON). MS m/z (rel int. %): 265 (10) (Mþ), 250 (94), 210 (100), 193
(12), 152 (5), 58 (42). Anal. Calcd for C17H31NO (265.44): C, 76.92; H,
11.77; N, 5.28. Found: C, 77.08; H, 11.95; N, 4.98. Rf (3% EtOAc/CHCl3)
0.58. Yellow viscous material.
4.6.9. ((Z)-Tridec-2-enoylamino)-acetic acid methyl ester (6d)
MS m/z (rel int. %): 283 (8) (Mþ), 252 (10), 195 (27), 194 (32), 152
(31), 131 (20), 81 (100), 55 (67) (obtained in catalytic mixture only).
4.6.4. (E)-1-(Piperidin-1-yl)-tridec-2-en-1-one (5b)
1H NMR (CDCl3)
d
: 6.78 (dt, J¼7.1, 15.1 Hz, 1H, ]CH), 6.20 (d,
Acknowledgements
J¼15.1 Hz, 1H, ]CH), 3.40–3.60 (m, 4H, N(CH2)2), 2.15 (q, J¼7.2 Hz,
2H, CH2), 1.58–1.63 (m, 2H, CH2), 1.48–1.55 (m, 4H, 2ꢂCH2), 1.40 (qi,
J¼7.2 Hz, 2H, CH2), 1.25 (br s, 14H, chain methylenes), 0.84 (t,
The authors thank the Hungarian Research Fund (NI61591) and
Johnson Matthey for the generous gift of palladium(II) acetate.
J¼6.8 Hz, 3H, CH3). 13C NMR (CDCl3)
d: 165.6, 145.8, 120.3, 46.8 (br),
43.0 (br), 32.5, 31.9, 29.6, 29.5, 29.4, 29.3, 29.2, 28.4, 26.6, 25.6, 24.6,
22.6,14.0. IR (KBr, (cmꢁ1)): 1659 (CON), 1620 (C]C). MS m/z (rel int.
%): 279 (16) (Mþ), 250 (4), 222 (3), 180 (12), 166 (100), 138 (63), 127
(30), 84 (30). Anal. Calcd for C18H33NO (279.47): C, 77.36; H, 11.90;
N, 5.01. Found: C, 77.28; H, 12.11; N, 4.88. Rf (10% EtOAc/CHCl3) 0.50.
Yellow viscous material.
References and notes
´
1. Skoda-Fo¨ldes, R.; Kollar, L. Curr. Org. Chem. 2002, 6, 1097–1119.
2. Applied Homogeneous Catalysis with Organometallic Compounds; Cornils, B.,
Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, 1996; Transition Metals for
Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, 1998;
Vols. I–II.
3. Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V. Carbonylation: Direct Synthesis
of Carbonyl Compounds; Plenum: New York, NY and London, 1991.
4. Ozawa, F.; Sugimoto, T.; Yamamoto, T.; Yamamoto, A. Organometallics 1984, 3,
692–697.
5. Son, T.; Yanagihara, H.; Ozawa, F.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1988, 61,
1251–1258.
6. Skoda-Fo¨ldes, R.; Kolla´r, L. Chem. Rev. 2003, 103, 4095–4129 and references
cited therein.
7. Horva´th, L.; Berente, Z.; Kolla´r, L. Lett. Org. Chem. 2007, 4, 236–238.
8. Kumar, K.; Zapf, A.; Michalik, D.; Tillack, A.; Heinrich, T.; Bottcher, H.; Arit, M.;
Beller, M. Org. Lett. 2004, 6, 7–10.
4.6.5. 1-(Piperidin-1-yl)-tridec-2-yn-1-one (7b)
1H NMR (CDCl3)
d
: 3.65 (br t, J¼5.6 Hz, 2H, NCH2), 3.53 (br t,
J¼5.6 Hz, 2H, NCH2), 2.32 (t, J¼7.2 Hz, 2H, CH2), 1.48–1.66 (m, 6H,
3ꢂCH2), 1.37 (br qi, J¼7.2 Hz, 2H, CH2), 1.25 (br s, 14H, chain
methylenes), 0.85 (t, J¼6.8 Hz, 3H, CH3). 13C NMR (CDCl3)
d: 153.1,
93.1, 73.9, 48.1, 42.2, 31.9, 29.5, 29.4, 29.3, 29.0, 28.9, 27.8, 26.4, 25.3,
24.5, 22.6, 18.9, 14.0. IR (KBr, (cmꢁ1)): 1632 (CON), 2240 (C^C). MS
m/z (rel int. %): 277 (3) (Mþ), 248 (5), 220 (7), 207 (21), 178 (5), 164
(55), 150 (100), 136 (12), 84 (40). Anal. Calcd for C18H31NO (277.45):
C, 77.92; H, 11.26; N, 5.05. Found: C, 77.81; H, 11.32; N, 4.92. Rf (10%
EtOAc/CHCl3) 0.74. Yellow viscous material.
9. Gabriele, B.; Plastina, P.; Salerno, G.; Mancuso, R.; Costa, M. Org. Lett. 2007, 9,
3319–3322.
10. Tojino, M.; Otsuka, N.; Fukuyama, T.; Matsubara, H.; Ryu, I. J. Am. Chem. Soc.
2006, 128, 7712–7713.
11. Trost, B. M.; Ameriks, M. K. Org. Lett. 2004, 6, 1745–1748.
12. Ju, J.; Jeong, M.; Moon, J.; Jung, H.; Lee, S. Org. Lett. 2007, 9, 4615–4618.
13. Arcadi, A. Carbonylation of Enolizable Ketones (Enol Triflates) and Iodoalkenes.
In Modern Carbonylation Methods; Kolla´r, L., Ed.; Wiley-VCH: Weinheim, 2008;
Chapter 9, pp 223–250.
14. Coleman, B. E.; Cwynar, V.; Hart, D. J.; Havas, F.; Mohan, J. M.; Patterson, S.;
Ridenour, S.; Schmidt, M.; Smith, E.; Wells, A. J. Synlett 2004, 1339–1342.
15. Takami, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2004, 6, 4555–4558.
16. Nonaka, T.; Okuda, Y.; Matsubara, S.; Oshima, K.; Utimoto, K.; Nozaki, H. J. Org.
Chem. 1986, 51, 4716–4718.
17. Yachi, K.; Shinokubo, H.; Oshima, K. Angew. Chem., Int. Ed. 1998, 37, 2515–2517.
18. Kitagawa, K.; Inoue, A.; Shinokubo, H.; Oshima, K. Angew. Chem., Int. Ed. 2000,
39, 2481–2483.
19. Kokotos, G.; Constantinou-Kokotou, V.; Noula, C.; Nicolaou, A.; Gibbons, W. A.
Int. J. Pept. Protein Res. 1996, 48, 160–166.
20. Kokotos, G.; Six, D.; Loukas, V.; Smith, T.; Constantinou-Kokotou, V.; Hadji-
pavlou-Litina, D.; Kotsovolou, S.; Chiou, A.; Beltzner, C.; Dennis, E. J. Med. Chem.
2004, 47, 3615–3628.
21. Six, D. A.; Barbayianni, E.; Loukas, V.; Constantinou-Kokotou, V.; Hadjipavlou-
Litina, D.; Stephens, D.; Wong, A. C.; Magrioti, V.; Moutevelis-Minakakis, P.;
Baker, S. F.; Dennis, E. A.; Kokotos, G. J. Med. Chem. 2007, 50, 4222–4235.
22. Yaksh, T. L.; Kokotos, G.; Svensson, C. I.; Stephens, D.; Kokotos, C. G.; Fitzsim-
mons, B.; Hadjipavlou-Litina, D.; Hua, X. Y.; Dennis, E. A. J. Pharmacol. Exp. Ther.
2006, 316, 466–475.
23. Hansford, K. A.; Reid, R. C.; Clark, C. I.; Tyndall, J. D. A.; Whitehouse, M. W.;
Guthrie, T.; McGeary, R. P.; Schafer, K.; Martin, J. L.; Fairlie, D. P. ChemBioChem
2003, 4, 181–185.
24. Amatore, C.; Carre, E.; Jutand, A.; M’Barki, M. A.; Meyer, G. Organometallics
1995, 14, 5605–5614 and references cited therein.
4.6.6. (E)-1-(Morpholin-4-yl)-tridec-2-en-1-one (5c)
1H NMR (CDCl3)
d
: 6.86 (dt, J¼7.1, 15.0 Hz, 1H, ]CH), 6.15 (d,
J¼15.0 Hz,1H, ]CH), 3.50–3.65 (m, 8H, 2ꢂ(CH2)2), 2.15 (q, J¼7.3 Hz,
2H, CH2), 1.40 (qi, J¼7.3 Hz, 2H, CH2), 1.25 (br s, 14H, chain methy-
lenes), 0.84 (t, J¼6.7 Hz, 3H, CH3). 13C NMR (CDCl3)
d: 165.8, 147.3,
119.3, 66.8, 46.0 (br), 42.2 (br), 32.6, 31.8, 29.6, 29.5, 29.4, 29.3, 29.2,
28.3, 22.6, 14.1. IR (KBr, (cmꢁ1)): 1660 (CON), 1624 (C]C). MS m/z
(rel int. %): 281 (17) (Mþ), 252 (5), 210 (6), 195 (23), 168 (32), 140
(100),129 (23),114 (12), 86 (32). Anal. Calcd for C17H31NO2 (281.44):
C, 72.55; H, 11.10; N, 4.98. Found: C, 72.39; H, 11.22; N, 4.80. Rf (30%
EtOAc/CHCl3) 0.45. Yellow viscous material.
4.6.7. 1-(Morpholin-4-yl)-tridec-2-yn-1-one (7c)
1H NMR (CDCl3)
d
: 3.60–3.72 (m, 8H, 2ꢂ(CH2)2), 2.32 (t,
J¼7.2 Hz, 2H, CH2), 1.54 (qi, J¼7.2 Hz, 2H, CH2), 1.32–1.40 (m, 2H,
CH2), 1.25 (br s, 12H, chain methylenes), 0.84 (t, J¼6.8 Hz, 3H, CH3).
13C NMR (CDCl3)
d: 153.4, 94.2, 73.3, 66.9, 66.5, 47.2, 41.8, 31.8, 29.5,
29.4, 29.3, 29.0, 28.9, 27.8, 22.6, 18.9, 14.1. IR (KBr, (cmꢁ1)): 2240
(C^C), 1650 (CON). MS m/z (rel int. %): 279 (6) (Mþ), 250 (12), 209
(58),166 (59),153 (45),123 (30), 86 (100). Anal. Calcd for C17H29NO2
(279.42): C, 73.07; H, 10.46; N, 5.01. Found: C, 72.88; H, 10.54; N,
4.89. Rf (20% EtOAc/CHCl3) 0.56. Yellow crystalline material, mp
40–41 ꢀC.
25. Csakai, Z.; Skoda-Foldes, R.; Kollar, L. Inorg. Chim. Acta 1999, 286, 93–97.
26. Skoda-Fo¨ldes, R.; Csa´kai, Z.; Kolla´r, L.; Horva´th, J.; Tuba, Z. Steroids 1995, 60,
812–816.
´
¨
´
27. Canty, A. J. Acc. Chem. Res. 1992, 25, 83–90.
4.6.8. ((E)-Tridec-2-enoylamino)-acetic acid methyl ester (5d)
28. Canty, A. J. Platinum Metals Rev. 1993, 37, 2–7.
29. Barton, D. H. R.; O’Brien, R. E.; Sternhell, S. J. Chem. Soc. 1962, 470–476.
30. Barton, D. H. R.; Bashiardes, B.; Fourrey, J. L. Tetrahedron Lett. 1983, 24,
1605–1608.
31. Oda, H.; Morizawa, Y.; Oshima, K.; Nozaki, H. Tetrahedron Lett. 1984, 25,
3221–3224.
1H NMR (CDCl3)
d
: 6.82 (dt, J¼7.1, 15.5 Hz, 1H, ]CH), 6.00 (br s,
1H, NH), 5.80 (d, J¼15.5 Hz, 1H, ]CH), 4.07 (d, J¼5.2 Hz, 2H,
CH2COO), 3.75 (s, 3H, OCH3), 2.15 (q, J¼7.3 Hz, 2H, CH2), 1.38–1.42
(m, 2H, CH2), 1.25 (br s, 14H, chain methylenes), 0.85 (t, J¼6.8 Hz,