1648
J. A. Miller et al.
PAPER
(3) Churchill, D.; Shin, J. H.; Hascall, T.; Hahn, J. M.;
Bridgewater, B. M.; Parkin, G. Organometallics 1999, 18,
2403.
(4) Taw, F. L.; White, P. S.; Bergman, R. G.; Brookhart, M. J.
Am. Chem. Soc. 2002, 124, 4192.
(5) (a) Miller, J. A.; Farrell, R. P. Tetrahedron Lett. 1998, 39,
6441. (b) Miller, J. A.; Farrell, R. P. Tetrahedron Lett. 1998,
39, 7275.
(6) This catalyst was prepared as described in the experimental
section. Alternatively, it can be purchased from Aldrich
(catalog number 56,767-1).
h. The reaction solution was cooled to r.t. and added to a solution of
4-methoxybenzonitrile (0.249 g, 1.88 mmol), dichlorobis(trimeth-
ylphosphine)nickel (0.029 g, 5.5 mol%) and tridecane (0.196 g,
1.07 mmol; internal GC standard) in THF (2 mL). The reaction mix-
ture was then heated at 60 °C for 15 h. A sample was withdrawn
from the reaction and quenched with sodium citrate (1 M) and Et2O.
GC analysis of the organic phase of the hydrolyzed reaction mixture
indicated the presence of 1-cyclopropyl-4-methoxybenzene (1.21
mmol, 64%) and cyclopropyl-(4-methoxyphenyl)methanone (0.21
mmol).
N-Phenylpiperidine (Table 3, Entry 1); Amines from Aryl Ni-
triles; Representative Procedure
(7) These results were obtained by GC analysis of a reaction
sample (containing tridecane as an internal standard)
quenched in a mixture of aq sodium citrate (1 M) and Et2O.
(8) A ‘spot test’9 confirmed the presence of cyanide ion in the aq
phase of the quenched reaction mixture.
(9) Feigl, F.; Anger, V. Analyst 1966, 91, 282.
(10) Among phosphines screened, the relative order of
effectiveness in this biaryl cross coupling reaction is: Me3P
>> Me2PPh = Et3P > MePPh2 = Me2PCH2CH2PMe2 > Ph3P
> (C6H11)3P.
A stirred mixture of Ni(CN)·4 H2O (0.054 g, 0.30 mmol), CsF (1.37
g, 9.0 mmol), and piperidine (1.0 g, 12 mmol) in anhyd THF (15
mL) was treated with BuLi (4.80 mL of 2.5 M solution; 11.7 mmol;
Aldrich) at r.t.. After stirring the mixture for 10 min, benzonitrile
(0.62 g, 6.0 mmol) and tridecane (0.55 g, 3.0 mmol; internal GC
standard) were added and the resultant dark brown reaction mixture
was heated to reflux. After stirring for 8 h at reflux, a sample was
withdrawn from the reaction and quenched in a mixture of sodium
citrate (1 M) and methyl tert-butyl ether. GC analysis of the organic
phase of the hydrolyzed reaction mixture indicated the presence of
N-phenylpiperidine (4.4 mmol, 73%), and no remaining benzoni-
trile or the corresponding amidine adduct.
(11) For a review of biaryl syntheses, see: Stanforth, S. P.
Tetrahedron 1998, 54, 2.
(12) Tamao, K.; Sumitani, K.; Kiso, Y.; Zembayashi, M.;
Fujioka, A.; Kodama, S.-I.; Nakajima, I.; Minato, A.;
Kumada, M. Bull. Chem. Soc. Jpn. 1976, 49, 1958.
(13) Desmarets, C.; Schneider, R.; Fort, Y. J. Org. Chem. 2002,
67, 3029; and references contained therein.
Acknowledgements
(14) For reviews, see: (a) Hartwig, J. F. Angew. Chem. Int. Ed.
1998, 37, 2046. (b) Muci, A. R.; Buchwald, S. L. Top. Curr.
Chem. 2002, 219, 131. (c) Hillier, A. C.; Grasa, G. A.;
Viciu, M. S.; Lee, H. M.; Yang, C.; Nolan, S. P. J.
Organomet. Chem. 2002, 653, 69.
The authors thank Professor Barry M. Trost (Stanford University)
for helpful discussions and Robert P. Farrell for experimental assi-
stance with this chemistry.
(15) (a) Kondo, Y.; Shilai, M.; Uchiyama, M.; Sakamoto, T. J.
Am. Chem. Soc. 1999, 121, 3539. (b) Krizan, T. D.; Martin,
J. C. J. Org. Chem. 1982, 47, 2681.
(16) For example, reaction of aryl oxazolines with POCl3 delivers
the corresponding benzonitriles in high yield: Dordor, I. M.;
Mellor, J. M.; Kennewell, P. D. Tetrahedron Lett. 1983, 24,
1437.
(17) For reviews of directed ortho metallation reactions, see:
(a) Sniekus, V. Chem. Rev. 1990, 90, 879. (b) Gschwend,
H. W.; Rodriguez, H. R. Org. React. 1979, 26, 1.
(18) Watson, S. C.; Eastham, J. F. J. Organomet. Chem. 1967, 9,
165.
(19) Mathis, M.; Harsha, W.; Hanks, T. W.; Bailey, R. D.;
Schimek, G. L.; Pennington, W. T. Chem. Mater. 1998, 10,
3568.
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Synthesis 2003, No. 11, 1643–1648 © Thieme Stuttgart · New York