96
I.P. Beletskaya et al. / Journal of Organometallic Chemistry 622 (2001) 89–96
4.2. Preparation of palladacycles
References
[1] (a) T. Mizoroki, K. Mori, A. Ozaki, Bull. Chem. Soc. Jpn. 44
(1971) 581. (b) R.F.Heck, J.P. Jr. Nolley, J. Org. Chem. 37
(1972) 2320. (c) R.F. Heck, Acc. Chem. Res. 12 (1979) 146. (d)
W. Cabri, I. Candiani, Acc. Chem. Res. 28 (1995) 2.
[2] (a) W.A. Herrmann, V.P.W. Bohm, C.-P. Reisinger, J.
Organomet. Chem. 576 (1999) 23. (b) W.A. Herrmann, C.
Brossmer, K. Ofele, C.-P. Reisinger, T. Priermeier, M. Beller, H.
Fischer, Angew. Chem. Int. Ed. Engl. 34 (1995) 1844. (c) W.A.
Herrmann, C. Brossmer, C.-P. Reisinger, T.H. Riermeier, K.
Ofele, M. Beller, Chem. Eur. J. 3 (1997) 1357. (d) M. Beller,
T.H. Riermeier, S. Haber, H.-J. Kleiner, W.A. Herrmann Chem.
Ber. 129 (1996) 1259.
Literature procedures were used for synthesis of com-
plexes 1 [2c], 13 [18], 14 [19], 15 [20], 16 [21], 17 [22], 18
[23], 19 [24], 20 [25], 21 [26], 23 [18].
4.3. [8-Quinolylmethyl](2,2%-dipyridyl)palladium(II)
chloride (22)
Complex 22 was prepared according to a previously
described procedure [24b]; Anal. Found: C, 54.21; H,
3.72; N, 9.78. Calc for C20H16N3PdCl (440.24): C,
54.57; H, 3.66; N, 9.54%.
[3] B.L. Shaw, S.D. Perera, E.A. Staley, Chem. Commun. (1998)
1361.
[4] D.A. Albisson, R.B. Bedford, P.N. Scully, Tetrahedron Lett. 39
(1998) 9793.
[5] (a) W. Cabri, I. Candiani, A. Bedeschi, R. Santi, Synlett. (1992)
871. (b) M. Ohff, A. Ohff, D. Milstein Chem. Commun. (1999)
357. (c) D.A. Alonso, C. Najera, M.C. Pacheco, Org. Lett. 2
(2000) 1823.
[6] A.S. Gruber, D. Zim, G. Eberling, A.L. Monteiro, J. Dupont,
Org. Lett. 2 (2000) 1287.
[7] M. Ohff, A. Ohff, M.E. van der Boom, D. Milstein, J. Am.
Chem. Soc. 119 (1997) 11687.
[8] I.P. Beletskaya, A.N. Kashin, N.B. Karlstedt, A.V. Chuchuri-
jkin, 10th IUPAC Symposium on Organo-Metallic Chemistry
directed toward Organic Synthesis, July 18–22, 1999, Versailles,
France, SL-28.
[9] K. Kiewel, Y. Liu, D.E. Bergbreiter, G.A. Sulikowski, Tetrahe-
dron Lett. 40 (1999) 8945.
[10] F. Miyaazaki, K. Yamaguchi, M. Shibasaki, Tetrahedron Lett.
40 (1999) 7379.
[11] D.E. Bergbreiter, P.L. Osburn, Y.-S. Liu, J. Am. Chem. Soc. 121
(1999) 9531.
[12] (a) M.T. Reetz, G. Lohmer, R. Schwickardi, Angew. Chem. Int.
Ed. 37 (1998) 481. (b) M.T. Reetz, E. Westermann, R. Lohmer,
G. Lohmer, Tetrahedron Lett. 39 (1998) 8449.
[13] (a) J. Louie, J.F. Hartwig, Angew. Chem. Int. Ed. Engl. 35
(1996) 2359. (b) M. Beller, T.H. Riermeier, Eur. J. Inorg. Chem.
(1998) 29.
[14] W.A. Herrmann, M. Elison, J. Fischer, C. Kocher, G.R.J. Artus,
Angew. Chem. Int. Ed. Engl. 34 (1995) 2371.
[15] B.L. Shaw, New J. Chem. 22 (1998) 77.
[16] F.-T. Luo, A. Jeevanandam, M.K. Basu, Tetrahedron Lett. 39
(1998) 7939.
[17] J. Tsuji, Acc. Chem. Res. 2 (1969) 144.
[18] G.E. Hartwell, R.V. Lawrence, M.J. Smas, J. Chem. Soc. (D).
(1970) 912.
[19] A. Kasahara, Bull. Chem. Soc. Jpn. 41 (1968) 1272.
[20] K. Hiraki, Y. Fuchita, K. Takechi, Inorg. Chem. 20 (1981) 4316.
[21] D.J. de Geest, B.J. O’Keefe, P.J. Steel, J. Organomet. Chem. 579
(1999) 97.
4.4. General procedure for the Heck reaction
Catalyst solution: the appropriate palladacycle (see
Scheme 3) was dissolved in 1 ml N,N-dimethylac-
etamide. The solution was purged with argon prior to
use. Reaction mixture: In a thermostated three-necked
flask installed on a magnetic stirrer, aryl halide (0.1
mmol), olefin (0.12 mmol), tri-n-butylamine (240 ml, 1
mmol), the solution of 1,4-di-t-butylbenzene (GLC in-
ternal standard) and N,N-dimethylacetamide (20 ml)
were placed while the flask being continously flushed
with argon. The reaction mixture was vigorously stirred
for 5 min and heated to 85°C. The catalyst solution
(about 10 ml) was injected by syringe into the preheated
reaction mixture. For kinetic studies, samples of 20–50
ml were withdrawn from the reaction mixture, mixed
with 1.5 ml 0.1 M HNO3 and titrated. To determine the
product yields aliquots of the reaction mixture were
diluted with 5% hydrochloric acid (1:5) and extracted
with methylene chloride (3×2 ml). The organic phases
were dried with anhydrous magnesium sulfate and ana-
lyzed by GLC.
The reactions with minimal loads of the palladium
catalyst were carried out in sealed glass ampoules. Aryl
halide (0.25 mmol), olefin (0.3 mmol), tri-n-butylamine
(0.25 mmol), a solution of 1,4-di-t-butylbenzene (GC
standard), N,N-dimethylacetamide (0.5 ml) and the cat-
alyst solution (about 10 ml) were placed in an ampoule.
The reaction mixture was thoroughly degassed with two
freeze-pump-thaw cycles, sealed and placed in a heating
bath. The work-up and analysis were performed as
specified above.
[22] A.G. Cope, E.C. Friedrich, C. Edwin, J. Am. Chem. Soc. 90
(1968) 909.
[23] A.D. Ryabov, G.M. Kazankov, Koord. Khim. (in russian) 12
(1986) 540.
[24] (a) H. Onoue, K. Minami, K. Nakagawa, Bull. Chem. Soc. Jpn.
43 (1970) 3480. (b) A.D. Ryabov, G.M. Kazankov, A.K. Yat-
simirsky, L.G. Kuz’mina, O. Yu. Burtseva, N.V. Dvortsova,
V.A. Polyakov, Inorg. Chem. 31 (1992) 3083.
[25] H. Horino, N. Inone, J. Org. Chem. 46 (1981) 4416.
[26] G.M. Kazankov, P.A. Posel’enov, A.D. Ryabov, A.K. Yat-
simirsky, Metallorg. Khim. (in russian) 4 (1991) 45.
Acknowledgements
Financial support by the Russian Foundation for
Basic Research (project Nos. 00-03-32766, 00-15-97406
and AO115) is gratefully acknowledged.
.