I. J. S. Fairlamb et al. / Tetrahedron 60 (2004) 5711–5718
5717
(
[
1
m/z): 827 [(Mþ1), 4%], 728 [(M2N-Succ), 32%], 629
((Ph P) Pd-1), 17%]; IR (CH Cl , cm ) 1723 and 1645;
3 2 2 2
Colquhoun, H. M.; Williams, D. J. J. Chem. Soc., Dalton
Trans. 1986, 813.
2
1
H NMR (400 MHz, CDCl ) 7.79 (12H, m), 7.34 (18H, m),
3
13. Very recently we have been investigating the catalytic
properties of bridged succinimide ‘anionic’ palladium(II)
complexes, see: Serrano, J. L.; Fairlamb, I. J. S.; S a´ nchez, G.;
Garc ´ı a, L.; P e´ rez, J.; Vives, J.; L o´ pez, G.; Crawforth, C. M.;
Taylor, R. J. K. Eur. J. Inorg. Chem. 2004. in press.
14. (a) Crawforth, C. M.; Burling, S.; Fairlamb, I. J. S.; Taylor,
R. J. K.; Whitwood, A. C. Chem. Commun. 2003, 2194.
(b) Crawforth, C. M.; Fairlamb, I. J. S.; Taylor, R. J. K.
Tetrahedron Lett. 2004, 45, 461.
3
1
1
.40 (4H, s, 2£CH2); P NMR (162 MHz, CDCl ) 20.42.
3
2
(
1
.1.3. Typical Suzuki reaction. Phenylboronic acid
50 mg, 0.41 mmol), bromobenzene (70.7 mg, 0.45 mmol,
.1 equiv.), Na CO (1 M (aq.), 1 ml), THF (1.5 mL) and
2
3
catalyst 1 (3.3 mg, 4.1 mmol, 1 mol%) were degassed via
three ‘freeze-pump-thaw’ cycles. The resulting mixture was
heated at 60 8C for the specified time. The reaction mixture
was allowed to cool to room temperature and water (10 mL)
added. The mixture was extracted with CH Cl (3£10 mL)
15. Roundhill, D. M. Inorg. Chem. 1970, 9, 254.
16. Amatore, C.; Broeker, G.; Jutand, A.; Khalil, F. J. Am. Chem.
Soc. 1997, 119, 5176.
2
2
and the organic extracts dried (MgSO ), filtered and
4
concentrated in vacuo. Purification by flash chromatography
gave biphenyl as a white solid (42.3 mg, 67%).
17. The X-ray structure of 2 has been deposited to the Cambridge
crystallographic database (UK): CCDC No. 228518.
1
8. Serrano, J. L.; Garc u´ a´ , L.; P e´ rez, J.; P e´ rez, E.; Vives, J.;
S a´ nchez, G.; L o´ pez, G.; Molins, E.; Orpen, A. G. Polyhedron
2
002, 21, 1589.
19. Response factors for GC analysis: 4-nitrobromobenzene, 1.00;
-nitrobiphenyl, 1.40; triphenylphosphine, 2.30: GC-MS
Acknowledgements
4
The University of York is thanked for funding through an
innovation and research priming fund grant (to I. J. S. F).
Dr. Adam F. Lee (York) is thanked for providing analytical
equipment and for use of his laboratory.
analysis of selected quenched samples was performed to
ascertain the identity of the components from the reaction
mixture. Linear correlations were seen for three separate
concentrations of each component. In the absence of the
palladium precatalyst 2, no reaction is observed under the
conditions used.
2
0. It is not possible to rule out the formation of higher order
polynuclear palladium species, whether they be palladium
clusters or colloids, which could be responsible for the
catalytic reaction. It should be noted that the formation of bis-
ligated palladium(0) species is not a prerequsite for the Suzuki
reaction—indeed mono-ligated palladium(0) is able to
catalyse the Suzuki reaction more effectively (higher turnover
frequencies) which is presumably associated with promoting
the rate determining transmetallation step, see: Beeby, B.;
Bettington, S.; Fairlamb, I. J. S.; Goeta, A. E.; Kapdi, A. R.;
Niemel a¨ , E. H.; Thompson, A. L. New J. Chem. 2004, 28,
600–605.
References and notes
1
. (a) Heck, R. F. Palladium Reagents in Organic Syntheses;
Academic: New York, 1985. (b) Tsuji, J. Palladium Reagents
and Catalysts; Wiley: Chichester, 1995.
2. Hartwig, J. F. Acc. Chem. Res. 1998, 31, 852, and references
cited therein.
3. Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100,
3
009.
4
. Negishi, E.; Anastasia, L. Chem. Rev. 2003, 103, 1979.
. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron
Lett. 1975, 16, 4467. (b) Tykwinski, R. R. Angew. Chem., Int.
Ed. 2003, 42, 1566. (c) Sonogashira, K. J. Organomet. Chem.
5
21. The higher catalyst loading was used to facilitate detection of
the phosphorus containing species.
2
002, 653, 46.
. (a) Milstein, D.; Stille, J. K. J. Am. Chem. Soc. 1978, 100,
636. (b) Stille, J. K. Angew. Chem. Int. Ed. 1986, 25, 508.
c) Farina, V.; Krishnamurthy, V.; Scott, W. J. Org. React.
997, 50, 1.
. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
b) Suzuki, A. J. Organomet. Chem. 1999, 576, 147. (c) Wolfe,
22. We have been unable to purify adduct 6 by regular silica-gel
column chromatography from this mixture.
6
3
23. To the best of our knowledge this complex has not been
synthesised independently. Given the fact that 4-nitro-phenyl
bromide is often used as a benchmark substrate in Pd-catalysed
cross-coupling reactions, this is surprising. All common
databases, including the Cambridge Crystallographic Data-
base, were searched for details of this complex.
(
1
7
(
J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am. Chem.
Soc. 1999, 121, 9550. (d) Suzuki, A. In Metal-Catalyzed
Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.;
VCH: Weinheim, 1998; p 49.
24. We have not isolated any palladium complexes (in a zero or
þtwo oxidation state) from silica-gel chromatography. No
yellow bands, which could be indicative of a palladium(II)
species, were also not seen.
8
9
. (a) Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41,
4176. (b) Bedford, R. B. Chem. Commun. 2003, 1787.
. Fagnou, K.; Lautens, M. Angew. Chem., Int. Ed. 2002, 41, 26,
and references cited therein.
25. (a) Coulson, D. R. Inorg. Synth. 1972, 13, 121. (b) King, R. B.;
Kapoor, P. N. Inorg. Chem. 1972, 11, 1524.
26. Mann, F. G.; Purdie, D. J. Chem. Soc. 1935, 1549.
27. Mathews, C. J.; Smith, P. J.; Welton, T. Chem. Commun. 2000,
1249.
1
1
1
0. (a) Amatore, C.; Jutand, A. Acc. Chem. Res. 2000, 33, 314.
b) Amatore, C.; Jutand, A. J. Organomet. Chem. 1999, 576,
54, and references cited therein.
1. (a) Nestler, B.; Uhligh, E. Z. Anorg. Allg. Chem. 1985, 530,
96. (b) Serrano, J. L.; Zheng, Y.; Dilworth, J. R.; S a´ nchez, G.
(
2
28. Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org.
Chem. 2002, 67, 5553.
1
29. Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am.
Chem. Soc. 1999, 121, 9550.
30. Littke, A. F.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 6989.
Inorg. Chem. Commun. 1999, 2, 407.
2. Adams, H.; Bailey, N. A.; Briggs, T. N.; McCleverty, J. A.;