Introduction of Allyl and Prenyl Side-Chains into Aromatic Systems
Palladium-Catalysed Cross-Coupling Reactions of Arylboronic Acids
with Allyl and Prenyl Bromides: All the reactions were carried out
by the same procedure. One experiment is described in detail to
illustrate the methods used. [Pd2(dba)3] (0.054 g, 7 mol-%), allyl
(DFG), and the Fonds der Chemischen Industrie (Germany). A
travel grant to J. C. P. from the Alexander von Humboldt Founda-
tion and fellowships to D. C. G. and S. D. M. for short stays in
Germany from Secretaria de Ciencia y Tecnica (SECyT) (Ar-
bromide (0.090 g, 0.75 mmol), K2CO3 (0.93 g, 9 equiv.), 4-biphen- gentina) and Deutscher Akademischer Austauschdienst (DAAD)
ylboronic acid (0.20 g, 1 mmol) and dry toluene (14 mL) were
placed in a two-necked round-bottom flask under argon. The reac-
tion mixture was heated at reflux for 15 h, monitoring by GC. Then
hydrogen peroxide (10 mL) was added, the mixture was stirred at
room temperature for 30 min and the toluene layer was separated.
The aqueous layer was extracted three times with Et2O. The com-
bined organic extracts were washed with brine and dried with
MgSO4. The solvent was removed under reduced pressure and the
crude product was purified by column chromatography on silica
gel (EtOAc/cyclohexane, 4:96) to give 4-allylbiphenyl (31) (0.138 g,
(Germany) are acknowledged.
[1] a) A. Suzuki, The Suzuki Reaction with Arylboron Compounds
in Arene Chemistry, in: Modern Arene Chemistry (Ed.: D. As-
truc), Wiley-VCH, Weinheim, 2002, p. 53; b) F. Diederich, P. J.
Stang (Eds.), Metal-catalyzed Cross-coupling Reactions, Wiley-
VCH, Weinheim, 1997; c) J. Tsuji, Palladium Reagents and Cat-
alysts, Wiley, Chichester, 1995.
[2] a) A. Suzuki, Acc. Chem. Res. 1982, 15, 178; b) N. Miyaura,
A. Suzuki, Chem. Rev. 1995, 95, 2457.
[3] a) N. Miyaura, K. Yamada, A. Suzuki, Tetrahedron Lett. 1979,
20, 3437; b) N. Miyaura, A. Suzuki, J. Chem. Soc., Chem. Com-
mun. 1979, 866.
[4] a) G. E. Keck, E. J. Enholm, J. B. Yates, Tetrahedron 1985, 41,
4079; b) V. Farina, Pure Appl. Chem. 1996, 68, 73; c) S. D.
Goldberg, R. H. Grubbs, Angew. Chem. Int. Ed. 2002, 41, 807.
[5] a) D. Bouyssi, V. Gerusz, G. Balme, Eur. J. Org. Chem. 2002,
2445; b) S. Kotha, M. Behera, V. R. Shah, Synlett 2005, 12,
1877; c) S. W. Wright, D. L. Hageman, L. D. McClure, J. Org.
Chem. 1994, 59, 6095.
1
0.71 mmol, 95%) as a brown oil. H NMR (CDCl3): δ = 3.28 (d,
J = 6.8 Hz, 2 H), 4.96–4.99 (m, 1 H), 5.95 (ddt, J = 16.8, 10.2,
6.8 Hz, 1 H), 7.09–7.46 (m, 9 H) ppm. 13C NMR (CDCl3): δ =
39.22, 115.75, 126.81, 127.29, 127.48, 128.25, 128.88, 136.15,
137.65, 139.96, 145.60 ppm. MS (EI, 70 eV): m/z (%) = 194 (100)
[M]+, 178 (34), 165 (36), 152 (20), 128 (5), 115 (19), 91 (5), 78 (11),
63 (5), 51 (6), 39 (14). HRMS (EI): calcd. for C15H14 194.1096;
found 194.1087.
4-Prenylbiphenyl (32): 1H NMR (CDCl3): δ = 1.74 (s, 3 H), 1.76 (s,
3 H), 3.05 (d, J = 6.7 Hz, 2 H), 5.25 (t, J = 6.7 Hz, 1 H), 7.06–7.48
(m, 9 H) ppm. 13C NMR (CDCl3): δ = 17.76, 25.65, 33.44, 120.68,
126.81, 127.02, 127.29, 128.88, 131.10, 136.17, 139.96, 141.95 ppm.
MS (EI, 70 eV): m/z (%) = 222 (100) [M]+, 207 (44), 192 (17), 179
(39), 165 (34), 152 (17), 129 (8), 115 (7), 91 (5), 78 (7), 63 (5), 56 (4),
41 (8). HRMS (EI): calcd. for C17H18 222.1409; found 222.1415.
[6] a) Y. Yamamoto, M. Takahashi, N. Miyaura, Synlett 2002,
1473; b) M. Stefinovic, V. Snieckus, J. Org. Chem. 1998, 63,
2808; c) S. J. Miller, H. E. Blackwell, R. H. Grubbs, J. Am.
Chem. Soc. 1996, 118, 9606; d) A. Okada, T. Ohshima, M.
Shibasaki, Tetrahedron Lett. 2001, 42, 8023; see also ref.[4]
.
[7] W. Dohle, F. Kopp, G. Cahierz, P. Knochel, Synlett 2001, 12,
1901.
[8] T. Ishiyama, M. Murata, N. Miyaura, J. Org. Chem. 1995, 60,
7508.
[9] a) M. Vaultier, B. Carboni, Comprehensive Organometallic
Chemistry II (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson),
Pergamon Press, Oxford, 1995, vol. 11, p. 191; b) W. R. Roush,
Comprehensive Organic Synthesis (Ed.: B. M. Trost), Pergamon
Press, Oxford, 1991, vol. 2, p. 1.
[10] a) E. J. Corey, C.-M. Yu, S. S. Kim, J. Am. Chem. Soc. 1989,
111, 5495; b) P. G. M. Wuts, S. S. Bigelow, J. Org. Chem. 1982,
47, 2498; c) R. W. Hoffmann, B. Kemper, Tetrahedron Lett.
1982, 23, 845.
[11] a) T. Watanabe, N. Miyaura, A. Suzuki, J. Organomet. Chem.
1993, 444, C1; b) R. W. Hoffmann, T. Sander, A. Hense, Lie-
bigs Ann. Chem. 1993, 771.
Palladium-Catalysed Cross-Coupling Reactions of Potassium Aryl-
trifluoroborates and Allyl and Prenyl Bromides: All the reactions
were carried out by the same procedure. One experiment is de-
scribed in detail to illustrate the methods used. A Schlenk flask was
charged with Pd(OAc)2 (0.010 g, 5 mol-%), allyl bromide (0.13 g,
1.08 mmol), potassium naphthalenetrifluoroborate (0.26 g,
1.29 mmol) and dry 1,4-dioxane (3 mL). The reaction mixture was
heated at 100 °C for 6 h and the progress of the reaction was moni-
tored by GC. The crude product was diluted with water (10 mL)
and the aqueous layer was extracted three times with Et2O. The
combined organic layers were washed with brine and dried with
MgSO4. The solvent was removed under reduced pressure and the
crude product was purified by column chromatography on silica
gel (n-hexane), to afford 1-allylnaphthalene (37; 0.15 g, 0.92 mmol,
85%) as an oily liquid. 1H NMR (CDCl3): δ = 3.81 (d, J = 6.3 Hz,
2 H), 5.05–5.10 (m, 2 H), 6.16–6.60 (m, 1 H), 7.31 (d, J = 6.9 Hz,
1 H), 7.37 (d, J = 7.2 Hz, 1 H), 7.42–7.51 (m, 2 H), 7.70 (d, J =
6.9 Hz, 1 H), 7.83 (t, J = 7.7 Hz, 1 H), 8.02 (d, J = 8.1 Hz, 1
H) ppm. 13C NMR (CDCl3): δ = 35.45, 114.38, 122.19, 123.68,
123.77, 123.96, 124.44, 125.13, 126.86, 130.16, 132.01, 133.17,
135.15 ppm. MS (EI, 70 eV): m/z (%) = 168 (100) [M]+, 167 (95),
153 (90), 141 (32), 128 (15), 115 (37), 102 (8), 83 (10), 63 (10),
51 (9), 39 (12). HRMS (EI): calcd. for C13H12 168.0939; found
168.0931.
[12] a) V. Nyzam, C. Belaud, J. Villieras, Tetrahedron Lett. 1993, 34,
6899; b) R. W. Hoffmann, G. Niel, Liebigs Ann. Chem. 1991,
1195.
[13] a) K. K. Wang, C. Liu, Y. Gu, F. N. Burnett, P. D. Sattsangi,
J. Org. Chem. 1991, 56, 1914; b) M. Satoh, Y. Nomoto, N.
Miyaura, A. Suzuki, Tetrahedron Lett. 1989, 30, 3789.
[14] a) M. Sato, Y. Yamamoto, S. Hara, A. Suzuki, Tetrahedron
Lett. 1993, 34, 7071; b) D. S. Matteson, D. Majumdar, Organo-
metallics 1983, 2, 1529.
[15] T. Ishiyama, T. A. Ahiko, N. Miyaura, Tetrahedron Lett. 1996,
37, 6889.
[16] W. G. Young, A. N. Prater, S. Winstein, J. Am. Chem. Soc.
1933, 55, 4908.
[17] a) R. A. Benkeser, Synthesis 1971, 347; b) J. E. Nordlander,
W. G. Young, J. D. Roberts, J. Am. Chem. Soc. 1961, 83, 494.
[18] a) E. Vedejs, R. W. Chapman, S. C. Fields, S. Lin, M. R.
Schrimpf, J. Org. Chem. 1995, 60; b) S. Darses, G. Michaud,
J.-P. Genêt, Eur. J. Org. Chem. 1999, 1875; c) S. Darses, G.
Michaud, J.-P. Genêt, Tetrahedron Lett. 1998, 39, 5045; d) S.
Darses, G. Michaud, J.-P. Genêt, J.-L. Brayer, J.-P. Demoute,
Tetrahedron Lett. 1997, 38, 4393.
Acknowledgments
This work was supported by Consejo Nacional de Investigaciones
Científicas y Técnicas (CONICET) (PIP 6095), Agencia Nacional
de Promoción Científica y Tecnológica (ANPCyT) (BID 1728/OC-
AR PICT N°2467), the Universidad Nacional del Sur (Bahía
Blanca, Argentina), the Deutsche Forschungsgemeinschaft
[19] a) J. P. Wolfe, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121,
9550; b) A. F. Littke, D. Chaoyang, G. C. Fu, J. Am. Chem.
Eur. J. Org. Chem. 2009, 3964–3972
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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