Stille coupling of 8 with vinyltin reagents
References
8 (1.60 g, 5 mmol), (E)-1-trimethylsilyl-2-n-tributylstannyl-
ethylene (2.14 g, 5.5 mmol) and 65 mg (0.25 mmol) of dichloro-
bis(acetonitrile)palladium(II) diluted in DMF (15 mL) were
mixed in a 50 mL flask. The mixture was stirred for 6 h at
25 ꢁC, then hydrolysed with 25 mL of a 1 M solution of potas-
sium fluoride and 25 mL of acetone to precipitate the tributyl-
tin iodide formed. After vigorous stirring for 2 h, the reaction
mixture was filtered, and extracted with diethyl ether. After the
usual work-up, the crude 10 were purified by column chroma-
tography on silica gel (petroleum ether–diethyl ether 95:5 as
eluant).
1
(a) J. T. Welch, Tetrahedron, 1987, 43, 3123 and references cited
therein; (b) R. Filler, Y. Kobayashi and L. Yagupolskii, Organo-
fluorine Compounds in Medicinal Chemistry and Biomedical Appli-
cations, Elsevier, Amsterdam, 1993; (c) R. E. Banks, B. E. Smart
and J. C. Tatlow, Organofluorine Chemistry-Principles and Com-
mercial Applications, Plenum Press, New York, 1994; (d ) M.
Hudlicky and A. E. Pavlath, Chemistry of Organic Fluorine Com-
pounds II-A Critical Review, American Chemistry Society,
Washington, DC, 1995; (e) R. D. Chambers, Organofluorine
Chemistry-Fluorinated Alkenes and Reactive Intermediates,
Springer-Verlag, Berlin, 1997; ( f ) T. Hiyama, Organofluorine
Compounds-Chemistry and Applications, Springer-Verlag, Berlin,
2000; (g) J. T. Welch and S. Eswara-Krishnan, Fluorine in Bio-
organic Chemistry, Wiley, New York, 1991.
Ethyl (2E,4E)-3-trifluoromethylhepta-2,4,6-trienoate (10a).
IR: 3085, 2976, 1726, 1632 cmꢀ1 1H NMR d: 1.28 (3H, t,
.
´
2
3
(a) A. Francesch, R. Alvarez, S. Lopez and A. R. de Lera, J. Org.
Chem., 1997, 62, 310; (b) M. Groesbeek and S. O. Smith, J. Org.
Chem., 1997, 62, 3638.
(a) V. P. Kukhar and V. A. Soloshonok, Fluorine-Containing Ami-
noacids, Synthesis and Properties, Wiley, New York, 1995; (b) A.
´
Bensadat, C. Felix, A. Laurent, E. Laurent, R. Faure and T.
Thomas, Bull. Soc. Chim. Fr., 1996, 133, 509.
(a) C. D. Poulter, P. L. Wiggins and T. L. Plummer, J. Org.
Chem., 1981, 46, 1532; (b) J. Legros, B. Crousse, D. Bonnet-
Delpon and J. P. Be´gue´, J. Fluorine Chem., 2001, 107, 121; (c)
J. P. Begue, D. Bonnet-Delpon and A. Kornilov, Org. Synth.,
1998, 76, 153; (d ) J. P. Be´gue´, D. Bonnet-Delpon, D. Mesureur,
G. Nee and S. W. Wu, J. Org. Chem., 1992, 57, 3807.
S. C. Welch and J. M. Gruber, J. Org. Chem., 1982, 47, 385.
J. B. Siddall, M. Biskup and J. H. Fried, J. Am. Chem. Soc., 1969,
91, 1853.
J ¼ 7.1 Hz), 4.21 (2H, q, J ¼ 7.1 Hz), 5.37 (1H, d, J ¼ 10.1
Hz), 5.46 (1H, d, J ¼ 16.5 Hz), 6.20 (1H, s), 6.44 (1H, dt,
J ¼ 16.5 Hz, J ¼ 10.1 Hz), 6.72 (1H, ddq, J ¼ 16.2 Hz,
J ¼ 10.1 Hz, JH–F ¼ 2.3 Hz), 7.45 (1H, d, J ¼ 16.2 Hz). 13C
NMR d: 14.1, 61.0, 119.7 (q, JC–F ¼ 6 Hz), 122.1, 122.5 (q,
JC–F ¼ 277 Hz), 123.2, 137.1 (q, JC–F ¼ 0.8 Hz), 139.2 (q,
JC–F ¼ 2 Hz), 140.4 (q, JC–F ¼ 29 Hz), 164.7 (q, JC–F ¼ 0.8
Hz). MS (70 eV) m/z: 220 (M+, 16), 175 (12), 147 (22), 127
(100), 79 (13), 78 (13), 51 (20), 39 (13). 19F NMR d: ꢀ67.1.
Anal. Calcd for C10H11F3O2 : C, 54.55; H, 5.04; found: C,
54.41; H, 5.05.
4
´
´
´
5
6
7
(a) D. Mead, A. E. Asato, M. Denny, R. S. H. Liu, Y. Hanzawa,
T. Taguchi, A. Yamada, N. Kobayashi, A. Hosoda and Y.
Kobayashi, Tetrahedron Lett., 1987, 28, 259 and references cited
therein; (b) R. Alvarez, B. Iglesias and A. R. De Lera, Tetrahe-
dron, 1999, 55, 13 779; (c) G. Shi, Y. Xu and M. Xu, Tetrahedron,
1991, 47, 1629; (d ) F.-L. Qing and J. Fan, J. Fluorine Chem., 1999,
96, 159.
Ethyl (2E,4E)-3-trifluoromethyl-6-methylhepta-2,4,6-tri-
enoate (10b). IR: 3070, 2970, 1720, 1625 cmꢀ1 1H NMR d:
.
1.30 (3H, t, J ¼ 7.1 Hz), 1.93 (3H, dd, J ¼ 1.2 Hz, J ¼ 0.8
Hz), 4.22 (2H, q, J ¼ 7.1 Hz), 5.24 (1H, q, J ¼ 0.8 Hz), 5.26
(1H, q, J ¼ 1.2 Hz), 6.21 (1H, s), 6.82 (1H, dq, J ¼ 16.9 Hz,
JH–F ¼ 2.3 Hz), 7.47 (1H, dq, J ¼ 16.9 Hz, JH–F ¼ 0.7 Hz).
13C NMR d: 14.1, 17.9, 61.0, 118.5, 119.5 (q, JC–F ¼ 6 Hz),
122.5 (q, JC–F ¼ 277 Hz), 122.7, 140.9 (q, JC–F ¼ 29 Hz),
141.1 (q, JC–F ¼ 2 Hz), 142.0 (q, JC–F ¼ 0.8 Hz), 164.9 (q,
JC–F ¼ 1 Hz). MS (70 eV) m/z: 234 (M+, 15), 189 (11), 165
(13), 161 (36), 141 (100), 109 (10), 51 (13), 41 (15), 39 (24).
19F NMR d: ꢀ66.9. Anal. Calcd for C11H13F3O2 : C, 56.41;
H, 5.59; found: C, 56.21; H, 5.47.
ˆ
(a) M. Abarbri, J.-L. Parrain and A. Duchene, Tetrahedron Lett.,
1995, 36, 2469; (b) M. Abarbri, J.-L. Parrain, J.-C. Cintrat and
8
9
ˆ
A. Duchene, Synthesis, 1996, 82; (c) J. Thibonnet, M. Abarbri,
J.-L. Parrain and A. Duchene, Tetrahedron Lett., 1996, 37, 7507.
ˆ
For initial results see: (a) F. L. Qing and Y. Zhang, Tetrahedron
´
Lett., 1997, 38, 6729; (b) G. Prie, J. Thibonnet, M. Abarbri, A.
Duchene and J.-L. Parrain, Synlett, 1998, 839; (c) J. Thibonnet,
ˆ
´
ˆ
G. Prie, M. Abarbri, A. Duchene and J.-L. Parrain, Tetrahedron
Lett., 1999, 40, 3151.
10 B. C. Hamper, Org. Synth., 1992, 70, 246.
`
11 J. C. Chalcat, F. Theron and R. Vessiere, C. R. Hebd. Seances
Acad. Sci., Ser. C, 1971, 273, 763.
12 J. P. Be´gue´, D. Bonnet-Delpon, D. Mesureur and M. Oure´vitch,
Magn. Reson. Chem., 1991, 29, 675.
Ethyl (2E,4E,6E)-3-trifluoromethyldodeca-2,4,6-trienoate
´
1
(10d). IR: 3060, 2950, 2920, 2840, 1720, 1615 cmꢀ1. H NMR
d: 0.87 (3H, t, J ¼ 6.1 Hz), 1.22–1.65 (6H, m), 1.29 (3H, t,
J ¼ 7.1 Hz), 2.14 (2H, dt, J ¼ 6.9 Hz), 4.21 (2H, q, J ¼ 7.1
Hz), 5.99 (1H, dt, J ¼ 6.9 Hz, J ¼ 15.1 Hz), 6.13 (1H, s),
6.18 (1H, dd, J ¼ 15.1 Hz, J ¼ 9.8 Hz), 6.72 (1H, ddq,
J ¼ 16.1 Hz, J ¼ 9.8 Hz, JH–F ¼ 2 Hz), 7.35 (1H, dq,
J ¼ 16.1 Hz, JH–F ¼ 0.7 Hz). 13C NMR d: 14.0, 14.1, 22.5,
28.5, 31.4, 33.0, 60.8, 118.1 (q, JC–F ¼ 6 Hz), 119.5, 122.6 (q,
JC–F ¼ 277 Hz), 130.8 (q, JC–F ¼ 1 Hz), 139.6 (q, JC–F ¼ 2
Hz), 141.0 (q, JC–F ¼ 29 Hz), 142.6, 165.0 (q, JC–F ¼ 0.8
Hz). 19F NMR d: ꢀ66.9. MS (70 eV) m/z: 290 (M+, 10), 267
(20), 265 (32), 262 (28), 246 (100), 233 (42), 221 (12), 219
(18), 45 (15), 43 (40). Anal. Calcd for C15H21F3O2 : C, 62.06;
H, 7.29; found: C, 62.21; H, 7.11.
13 For the addition of lithium halides on esters (amides or nitriles) or
exclusively on propiolic acid and phenylpropiolic acid using the
LiX–HOAc–solvent system, see: (a) S. Ma and X. Lu, J. Chem.
Soc., Chem. Commun., 1990, 1643; (b) S. Ma, X. Lu and Z. Li,
J. Org. Chem., 1992, 57, 709; (c) C. Meyer, I. Marek and J. F.
Normant, Synlett, 1993, 386; (d ) E. Piers, T. Wong, P. Coish
and C. Rogers, Can. J. Chem., 1994, 72, 1816; (e) F. Luo and
L. Hseih, J. Chin. Chem. Soc., 1994, 41, 871; ( f ) X. Lu, Z. Wang
and J. Ji, Tetrahedron Lett., 1994, 35, 613; (g) M. Kotora and
E. Negishi, Synthesis, 1997, 121.
14 (a) J. K. Stille, Angew. Chem., Int. Ed. Engl., 1986, 25, 508; (b)
T. N. Mitchell, Synthesis, 1992, 803; (c) V. Farina, in Comprehen-
sive Organometallic Chemistry II, eds. E.W. Abel, F. G. Stone and
G. Wilkinson, Pergamon Press, New York, 1995, vol. 12, ch. 3.4,
pp. 161–241; (d ) V. Farina and G. P. Roth, in Advances in Metal-
Organic Chemistry, ed. L. S. Liebeskind, JAI Press, New York,
1996, vol. 5, pp. 1–53; (e) V. Farina, V. Krishnamurthy and
W. J. Scott, Org. React., 1997, 50, 1; ( f ) V. Farina and V.
Krishnamurthy, The Stille Reaction, Wiley, New York, 1999.
15 (a) J. S. Xiang, A. Mahadevan and P. L. Fuchs, J. Am. Chem.
Soc., 1996, 118, 4284; (b) J. Thibonnet, Ph.D. Thesis, Tours,
France, 1999.
Ethyl (2E,4E,6E,8E)-3,8-bis(trifluoromethyl)deca-2,4,6,8-
tetraene-1,10-dioate (10e). IR: 3072, 2965, 2856, 1724, 1629
cmꢀ1
.
1H NMR d: 1.31 (6H, t, J ¼ 7.1 Hz), 4.21 (4H, q,
J ¼ 7.1 Hz), 6.29 (2H, s), 6.84 (2H, d, J ¼ 14.3 Hz), 7.68
(2H, d, J ¼ 14.3 Hz). 13C NMR d: 14.1 (2C), 61.3 (2C),
121.2 (2C, q, JC–F ¼ 6.0 Hz), 122.3 (2C, q, JC–F ¼ 277 Hz),
126.4 (2C), 138.3 (2C), 139.9 (2C, q, JC–F 29 Hz), 164.6 (2C,
q, JC–F ¼ 0.7 Hz). MS (70 eV) m/z: 386 (M+, 13), 285 (18),
313 (22), 293 (23), 267 (38), 265 (48), 248 (27), 239 (17), 217
(18), 199 (16), 171 (17), 169 (16), 152 (34), 151 (100), 150 (15),
45 (12). 19F NMR d: ꢀ67.0. Anal. Calcd for C16H16F6O4 : C,
49.75; H, 4.17; found: C, 49.71; H, 4.05.
ˆ
16 J. Thibonnet, M. Abarbri, J.-L. Parrain and A. Duchene, Main
Group Metal Chem., 1997, 20, 195.
17 PM3 calculations were performed by the Hyperchem package on
a PC computer. (rms energy gradient < 0.001). Partial charges of
the carbon atom bearing the tributylstannyl group: 3f ꢀ0.298, 3f 0
ꢀ0.334.
440
New J. Chem., 2003, 27, 432–441