5285
H-50), 7.46 (1H, m, H-40), 7.38 (1H, ddd, J=7.5, 7.3 and 0.8 Hz, H-7), 7.32 (2H, m, H-20 and H-60), 7.31 (1H, m,
H-6), 6.45 (1H, d, J=7.9 Hz, H-5), 2.75 (2H, t, J=7.3 Hz, H-11), 1.49 (2H, m, sext, J=7.3 Hz, H-12), 0.97 ppm
(3H, t, J=7.3 Hz, H-13). A NOESY experiment showed the presence of cross-peaks between the resonances of
the following protons: H-5 and H-20; H-5 and H-30; H-6 and H-30; H-60 and H-11; H-60 and H-12; H-60 and H-13.
13C NMR (150 MHz, CDCl3): ꢁ 167.23 (C-1), 142.47 (C-3), 138.75 (C-4), 137.78 (C-10), 133.78 (C-6), 129.24 (C-30),
129.24 (C-50), 129.10 (C-60), 129.10 (C-20), 129.10 (C-7), 128.51 (C-40), 127.45 (C-10), 125.47 (C-9), 125.12 (C-8),
122.72 (C-5), 35.68 (C-11), 20.72 (C-12), 13.87 ppm (C-13). Compound 6a (R1=C3H7; R2=Ph) had: mp 83±
86ꢀC. IR (KBr): ꢀ 1722, 1637, 1100, 777, 767, 709, 687 cm^1. 1H NMR (600 MHz, CDCl3): ꢁ 8.33 (1H, ddd,
J=7.9, 1.4 and 0.5 Hz, H-9), 7.58 (1H, ddd, J=8.0, 7.2 and 1.4 Hz, H-7), 7.48 (2H, m, H-30 and H-50), 7.45
(1H, m, H-8), 7.43 (1H, m, H-40), 7.25 (2H, m, H-20 and H-60), 6.94 (1H, ddd, J=8.0, 1.4 and 0.5 Hz, H-6),
2.34 (2H, t, J=7.5 Hz, H-11), 1.68 (2H, sext, J=7.5 Hz, H-12), 0.86 ppm (3H, t, J=7.5 Hz, H-13). A NOESY
experiment showed the presence of cross-peaks between the resonances of the following protons: H-6 and
H-20; H-60 and H-11; H-60 and H-12; H-60 and H-13. 13C NMR (150 MHz, CDCl3): ꢁ 162.79 (C-1), 154.97 (C-3),
138.83 (C-5), 134.49 (C-7), 134.38 (C-10), 130.66 (C-20), 130.66 (C-60), 129.42 (C-9), 128.91 (C-30), 128.91 (C-50),
128.08 (C-40), 127.38 (C-8), 124.75 (C-6), 120.05 (C-10), 116.39 (C-4), 33.23 (C-11), 20.97 (C-12), 13.63 ppm
(C-13).
5. Ma, S.; Shi, Z. J. Org. Chem. 1998, 63, 6387±6389.
6. (a) Arcadi, A.; Burini, A.; Cacchi, S.; Del Mastro, M.; Marinelli, F.; Pietroni, B. R. J. Org. Chem. 1992, 57, 976±
982; (b) Boussy, D.; Gore, J.; Balme, G. Tetrahedron Lett. 1992, 33, 2811±2814; (c) Boussy, D.; Gore, J.; Balme,
G.; Louis, D.; Wallach, J. Tetrahedron Lett. 1993, 34, 3129±3130; (d) Wang, Z.; Lu, X. J. Org. Chem. 1996, 61,
2254±2255; (e) Wu, M.-J.; Wei, L.-M.; Lin, C.-F. 10th Symposium on Organometallic Chemistry directed towards
Organic Synthesis; Versailles, France, 18±22 July 1999, Abstracts P-521.
7. These compounds were synthesized in 80±90% overall yield by reaction of methyl (Z)-3-bromopropenoate with
1.2 equiv. of a 1-alkyne in Et3N at 20ꢀC in the presence of 2 mol% PdCl2(PPh3)4 and 4 mol% CuI, followed by
saponi®cation of the so obtained methyl (Z)-2-en-4-ynoates with 1 M LiOH at 20ꢀC and acidi®cation of the
resulting lithium carboxylates.
8. Compounds 10, 11 and 12 gave satisfactory IR, MS, NMR and analytical data. As an example the physical and
spectral data of compounds 11b and 10b are given. Compound 11b had: MS, m/z (%): 243 (17), 214 (16), 200
(100), 187 (28), 172 (35), 144 (26), 118 (16). IR (®lm): ꢀ 1780, 1757, 1549, 1479, 1108, 888, 813 cm^1. 1H NMR (600
MHz, CDCl3): ꢁ 8.51 (1H, d, J=2.1 Hz, H-15), 7.84 (1H, d, J=5.6 Hz, H-4), 7.57 (1H, dd, J=8.0 and 2.1 Hz, H-
13), 7.30 (1H, d, J=8.0 Hz, H-12), 6.21 (1H, d, J=5.6 Hz, H-3), 2.88 (2H, quint, J=7.4 Hz, H-7), 2.39 (3H, s, H-
16), 1.43 (2H, quint, J=7.4 Hz, H-8) 1.35 (2H, sext, J=7.4 Hz, H-9), 0.87 ppm (3H, t, J=7.4 Hz, H-10). A
NOESY experiment showed the presence of cross-peaks between the resonances of the following protons: H-4 and
H-12, H-12 and H-7, H-12 and H-8, H-12 and H-9. 13C NMR (150 MHz, CDCl3): ꢁ 169.82 (C-2), 152.28 (C-11),
149.89 (C-15), 149.29 (C-5), 143.14 (C-4), 137.48 (C-13), 132.94 (C-14), 128.30 (C-6), 123.36 (C-12), 119.88 (C-3),
30.60 (C-8), 30.19 (C-7), 22.64 (C-9), 18.25 (C-16), 13.81 ppm (C-10). Compound 10b had: MS, m/z (%): 243 (10),
214 (20), 201 (100), 186 (24), 158 (19), 130 (17), 77 (14). IR (®lm): ꢀ 1735, 1566, 1547, 1088, 1071, 1015, 825 cm^1.
1H NMR (600 MHz, CDCl3): ꢁ 8.50 (1H, d, J=2.1 Hz, H-15), 7.56 (1H, dd, J=8.0 and 2.1 Hz, H-13), 7.55 (1H,
d, J=9.5 Hz, H-4), 7.21 (1H, d, J=8.0 Hz, H-12), 6.26 (1H, d, J=9.5 Hz, H-3), 2.66 (2H, t, J=7.3 Hz, H-7), 2.83
(3H, s, H-16), 1.70 (2H, quint, J=7.3 Hz, H-8), 1.31 (2H, sext, J=7.3 Hz, H-9), 0.86 ppm (3H, t, J=7.3 Hz, H-
10). 13C NMR (150 MHz, CDCl3): ꢁ 164.83 (C-6), 162.26 (C-2), 150.20 (C-15), 149.99 (C-11), 146.23 (C-4), 137.36