PHENYLCOPPER 1
can also be improved by the presence of Dimethyl Sulfide.6 See
Phenylcopper1
also Phenylcopper Boron Trifluoride Etherate.
PhCu
Biaryl Synthesis. Although arylcoppers are not typically used
for the synthesis of unsymmetrical biaryls, a combination of
[3220-49-3] C6H5Cu (MW 140.66) phenylcopper and 2-iodopyridine, or 2-pyridylcopper and an
iodoarene, provides 2-arylpyridines in good yield.4b
InChI = 1/C6H5.Cu/c1-2-4-6-5-3-1;/h1-5H;/rC6H5Cu/c7-6-4-2
-1-3-5-6/h1-5H
InChIKey = RIUFSTRETWGIIW-DCWWSCNNAF
1. (a) Normant, J. F., Synthesis 1972, 63. (b) Posner, G. H., Org. React.
(nucleophilic reagent for substitution reactions;1a,b selective re-
1975, 22, 253. (c) Posner, G. H., Org. React. 1972, 19, 1. (d) Taylor, R.
agent for conjugate additions;1a,c,d,2 couples with aryl halides to
J. K., Synthesis 1985, 364.
form biaryls3)
2. House, H. O.; Respess, W. L.; Whitesides, G. M., J. Org. Chem. 1966,
31, 3128.
Alternate Name: copper phenyl.
3. (a) Nilsson, M.; Wennerström, O., Tetrahedron Lett. 1968, 3307.
ć%
Physical Data: slightly yellow solid; mp 100 C (dec).13
(b) Nilsson, M.; Wennerström, O., Acta Chem. Scand. 1970, 24, 482.
Solubility: insol ether, tetrahydrofuran.
(c) Fanta, P. E., Synthesis 1974, 9.
Preparative Methods: phenylcopper and other arylcopper species
4. (a) Costa, G.; Camus, A.; Gatti, L.; Marsich, N., J. Organomet. Chem.
are most commonly prepared from equimolar amounts of alkyl- 1966, 5, 568. (b) Malmberg, H.; Nilsson, M., Tetrahedron 1986, 42,
3981. (c) Truce, W. E.; Lusch, M. J., J. Org. Chem. 1978, 43, 2252.
lithium or Grignard reagent and purified copper(I) halide in
(d) Westmijze, H.; Vermeer, P., Synthesis 1979, 390. (e) Ruitenberg, K.;
ether or THF.4 Arylcoppers can be prepared from the corre-
Westmijze, H.; Kleijn, H.; Vermeer, P., J. Organomet. Chem. 1984, 277,
sponding aryl halides and highly active zerovalent Copper.5
227.
Handling, Storage, and Precautions: decomposes on heating in
5. (a) Ebert, G. W.; Rieke, R. D., J. Org. Chem. 1984, 49, 5280. (b) Ebert,
solution. Hydrolyzed by H2O.13 Use in a fume hood.
G. W.; Rieke, R. D., J. Org. Chem. 1988, 53, 4482. (c) Rieke, R. D.;
Wehmeyer, R. M.; Wu, T.-C.; Ebert, G. W., Tetrahedron 1989, 45, 443.
6. Bertz, S. H.; Dabbagh, G., Tetrahedron 1989, 45, 425.
7. Kawashima, M.; Sato, T.; Fujisawa, T., Tetrahedron 1989, 45, 403.
8. Heckmann, B.; Mioskowski, C.; Yu, J.; Falck, J. R., Tetrahedron Lett.
Nucleophilic Substitutions. Arylcoppers are suitable
1992, 33, 5201.
nucleophiles for reaction with acid chlorides (to prepare aryl
9. Kang, J.; Cho, W.; Lee, W. K., J. Org. Chem. 1984, 49, 1838.
ketones),.5,6 primary alkyl halides,5a,b epoxides,5c ²-lactones
10. Westmijze, H.; Kleijn, H.; Vermeer, P., Synthesis 1978, 454.
(to prepare ²-aryl carboxylic acids),7 and 1,3-dioxolan-4-ones
11. Hutchinson, D. K.; Hardinger, S. A.; Fuchs, P. L., Tetrahedron Lett. 1986,
(to prepare protected secondary alcohols).8 Arylcopper species
27, 1425.
favor SN2 substitutions of allylic bromides9 and propargyl
12. (a) Matsuzawa, S.; Horiguchi, Y.; Nakamura, E.; Kuwajima, I.,
sulfonates.4d See also Methylcopper.
Tetrahedron 1989, 45, 349. (b) Bergdahl, M.; Lindstedt, E.-L.; Nilsson,
M.; Olsson, T., Tetrahedron 1988, 44, 2055. (c) Bergdahl, M.; Lindstedt,
Conjugate Additions. Phenylcopper will add in Michael fash- E.-L.; Nilsson, M.; Olsson, T., Tetrahedron 1989, 45, 535.
ion to conjugated enones,.6 cyanoalkynes,10 alkynyl sulfoxides,4c 13. Dictionary of Organometallic Compounds, 2nd ed.; Macintyre, J. E.,
and alkenyl sulfones.11 When performed in the presence of Ed.; Chapman and Hall: New York, 1995; Vol. 1, p 1079.
Chlorotrimethylsilane12a,b or Iodotrimethylsilane,12b,c Michael
addition of arylcoppers to enones, enals, and enoates is acceler- John N. Haseltine
ated and 1,4-selectivity (vs. 1,2) is enhanced. Rate and selectivity Georgia Institute of Technology, Atlanta, GA, USA
Avoid Skin Contact with All Reagents