SYNTHESIS
October 1998
1549
2-Vinylaniline:36
coupling of aryl halides with organostannanes is seen in ref-
erence 12. Phosphine inhibition is observed also in the coupling
of arylboronic acid, see:
1H NMR (CDCl3): δ = 3.74 (s, 2 H), 5.31 (d, J = 11.0 Hz, 1 H), 5.63
(d, J = 17.4 Hz, 1 H), 6.61–6.89 (m, 3 H), 7.01–7.18 (m, 1 H), 7.22–
7.37 (m, 1 H).
Wallow, T. I.; Novak, B. M. J. Org. Chem. 1994, 59, 5034.
(14) The yield was determined by 19F NMR. 19F NMR (CDCl3): for
1a: δ = 12.64; 1b: δ = 12.87; 1c: δ = 13.03; 1d: δ = 12.99, 2.95;
3a: δ = 13.10; 3b: δ = 13.30; 3c: δ = 12.85.
(15) A Ni(0) complex coordinated by 1,1'-(diphenylphosphino)fer-
rocene was used effectively as a catalyst for the cross-coupling
reaction of arylboronic acid with aryl chlorides.
Saito, S.; Sakai, M.; Miyaura, N. Tetrahedron Lett. 1996, 37,
2993.
4-Vinylthioanilsole:37
1H NMR (CDCl3): δ = 2.48 (s, 3 H), 5.22 (d, J = 11.0 Hz, 1 H), 5.71
(d, J = 17.8 Hz, 1 H), 6.68 (dd, J = 17.8, 11.0 Hz, 1 H), 7.15–7.46 (m,
4 H).
4-Vinylacetophenone:33
1H NMR (CDCl3): δ = 2.59 (s, 3 H), 5.39 (dd, J = 11.0, 0.7 Hz, 1 H),
5.87 (dd, J = 17.6, 0.7 Hz, 1 H), 6.75 (dd, J = 17.6, 11.0 Hz, 1 H),
7.41–7.56 (m, 2 H), 7.84–8.00 (m, 2 H).
Saito, S.; Oh-tani, O.; Miyaura, N. J. Org. Chem. 1997, 62,
8024.
(16) A similar competitive experiment in the palladium-catalyzed
coupling of a vinylstannane with p- and o-(trifluoromethanesul-
fonyl)acetophenone gave the para derivative as the main prod-
uct in a ratio of 73 to 27.
2-Vinylacetophenone:38
1H NMR (CDCl3): δ = 2.58 (s, 3 H), 5.34 (dd, J = 10.9, 1.3 Hz, 1 H),
5.64 (dd, J = 17.4, 1.3 Hz, 1 H), 7.20 (dd, J = 17.4, 10.9 Hz, 1 H),
7.28–7.68 (m, 4 H).
Farina, V.; Baker, S. R.; Benigni, D. A.; Hauck, S. I.; Sapino,
Jr., C. J. Org. Chem. 1990, 55, 5833.
(17) Seyferth, D.; Stone, F. G. A. J. Am. Chem. Soc. 1957, 79, 515.
(18) Logue, M. W.; Teng, K. J. Org. Chem. 1982, 47, 2549.
(19) Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 105, 6129.
(20) Groh, B. L. Tetrahedron Lett. 1991, 32, 7647.
(21) Jones, K.; Lappert, M. F. Proc. Chem. Soc. 1964, 22.
(22) Allen, D. W.; Tayler, B. F. J. Chem. Soc., Dalton Trans. 1982,
51.
(23) Baldwin, J. E.; Kapecki, J. A. J. Am. Chem. Soc. 1970, 92, 4869.
(24) Benedetto, S. D.; Consiglio, G. Helv. Chim. Acta. 1997, 80,
2204.
a
Present address: Graduate School of Material Science, Japan Ad-
vanced Institute of Science and Technology, Hokuriku, 1-1 Asahi-
dai, Tatsunokuchi, Ishikawa 923-1292, Japan.
(1) Farina, V. In Comprehensive Organometallic Chemistry II;
Abel, E. W.; Stone, F. G. A.; Wilkinson, G., Ed.; Pergamon:
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(2) For reviews, see:
Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
Mitchell, T. N. Synthesis 1992, 803.
Ritter, K. Synthesis 1993, 735.
(25) Kiplinger, J. L.; King, M. A.; Fechtenkötter, A.; Arif, A. M.;
Richmond, T. G. Organometallics 1996, 15, 5292.
(3) For a review, see: Farina, V. Pure Appl. Chem. 1996, 68, 73.
(4) We reported another approach to an active catalyst for this cou-
pling reaction. Shirakawa, E.; Yoshida, H.; Takaya, H. Tetrahe-
dron Lett. 1997, 38, 5177.
(5) In a series of pioneering works by Migita, Kosugi and their co-
workers concerning the transition metal-catalyzed coupling of
organostannanes, a rhodium complex was used as a catalyst.
Kosugi, M.; Shimizu Y.; Migita, T. J. Organomet. Chem. 1977,
129, C36.
(26)
1 1991, 1099.
(27) Efange, S. M. N.; Michelson, R. H.; Dutta, A. K.; Parsons, S. M.
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(33) Echavarren, A, M.; Stille, J, K. J. Am. Chem. Soc. 1987, 109,
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(6) Nickel catalysts are widely used for the cross-coupling reaction
of Grignard reagents. See:
Tamao, K.; Sumitani K.; Kumada, M. J. Am. Chem. Soc. 1972,
94, 4374.
Tamao, K.; Sumitani, K.; Kiso, Y.; Zembayashi, M.; Fujioka,
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Soc. Chem. Jpn. 1976, 49, 1958.
(7) Percec, V.; Bae, J.-Y.; Hill, D. H. J. Org. Chem. 1995, 60, 6895.
(8) A part of this study is already reported. Shirakawa, E.; Yamasa-
ki, K.; Hiyama, T. J. Chem. Soc., Perkin Trans. 1 1997, 2449.
(9) Kosugi, M.; Sasazawa, K.; Shimizu, Y.; Migita, T. Chem. Lett.
1977, 301.
(34) Hollywood, F.; Suschitzky, H. Synthesis 1982, 8, 662.
(35) Tzeng, Y. L.; Yang, P. F.; Mei, T. M.; Yuan, T. M.; Yu, C. C.;
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(10) For a review of the transformation of chloroarene catalyzed by
transition metal complexes, see:
(37) Hamer, G. K.; Peat, I. R.; Reynolds, W. F. Can. J. Chem. 1973,
51, 897.
Grushin, V. V.; Alper, H. Chem. Rev. 1994, 94, 1047.
(11) 19F NMR (CDCl3): for 1a: δ = 12.64; 3a: δ = 13.10.
(12) Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585.
(13) An example of phosphine inhibition in the palladium-catalyzed
(38) Hirao, A.; Kato, K.; Nakahama, S. Macromolecules 1992, 25,
535.