PHENYLCOPPER

1

Phenylcopper

1

PhCu

[3220-49-3]

C

6

H

5

Cu

(MW 140.66)

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

(nucleophilic reagent for substitution reactions;

1a,b

selective re-

agent for conjugate additions;

1a,c,d,2

couples with aryl halides to

form biaryls

3

)

Alternate Name:

copper phenyl.

Physical Data:

slightly yellow solid; mp 100

◦

C (dec).

13

Solubility:

insol ether, tetrahydrofuran.

Preparative Methods:

phenylcopper and other arylcopper species

are most commonly prepared from equimolar amounts of alkyl-
lithium or Grignard reagent and purified copper(I) halide in
ether or THF.

4

Arylcoppers can be prepared from the corre-

sponding aryl halides and highly active zerovalent Copper.

5

Handling, Storage, and Precautions:

decomposes on heating in

solution. Hydrolyzed by H

2

O.

13

Use in a fume hood.

Nucleophilic

Substitutions.

Arylcoppers

are

suitable

nucleophiles for reaction with acid chlorides (to prepare aryl
ketones),.

5,6

primary alkyl halides,

5a,b

epoxides,

5c

β

-lactones

(to prepare β-aryl carboxylic acids),

7

and 1,3-dioxolan-4-ones

(to prepare protected secondary alcohols).

8

Arylcopper species

favor S

N

2

′

substitutions of allylic bromides

9

and propargyl

sulfonates.

4d

See also Methylcopper.

Conjugate Additions. Phenylcopper will add in Michael fash-

ion to conjugated enones,.

6

cyanoalkynes,

10

alkynyl sulfoxides,

4c

and alkenyl sulfones.

11

When performed in the presence of

Chlorotrimethylsilane

12a,b

or Iodotrimethylsilane,

12b,c

Michael

addition of arylcoppers to enones, enals, and enoates is acceler-
ated and 1,4-selectivity (vs. 1,2) is enhanced. Rate and selectivity

can also be improved by the presence of Dimethyl Sulfide.

6

See

also Phenylcopper–Boron Trifluoride Etherate.

Biaryl Synthesis. Although arylcoppers are not typically used

for the synthesis of unsymmetrical biaryls, a combination of
phenylcopper and 2-iodopyridine, or 2-pyridylcopper and an
iodoarene, provides 2-arylpyridines in good yield.

4b

1.

(a) Normant, J. F., Synthesis 1972, 63. (b) Posner, G. H., Org. React.
1975, 22, 253. (c) Posner, G. H., Org. React. 1972, 19, 1. (d) Taylor, R.
J. K., Synthesis 1985, 364.

2.

House, H. O.; Respess, W. L.; Whitesides, G. M., J. Org. Chem. 1966,
31

, 3128.

3.

(a) Nilsson, M.; Wennerström, O., Tetrahedron Lett. 1968, 3307.
(b) Nilsson, M.; Wennerström, O., Acta Chem. Scand. 1970, 24, 482.
(c) Fanta, P. E., Synthesis 1974, 9.

4.

(a) Costa, G.; Camus, A.; Gatti, L.; Marsich, N., J. Organomet. Chem.
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.
(d) Westmijze, H.; Vermeer, P., Synthesis 1979, 390. (e) Ruitenberg, K.;
Westmijze, H.; Kleijn, H.; Vermeer, P., J. Organomet. Chem. 1984, 277,
227.

5.

(a) Ebert, G. W.; Rieke, R. D., J. Org. Chem. 1984, 49, 5280. (b) Ebert,
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.
1992, 33, 5201.

9.

Kang, J.; Cho, W.; Lee, W. K., J. Org. Chem. 1984, 49, 1838.

10.

Westmijze, H.; Kleijn, H.; Vermeer, P., Synthesis 1978, 454.

11.

Hutchinson, D. K.; Hardinger, S. A.; Fuchs, P. L., Tetrahedron Lett. 1986,
27

, 1425.

12.

(a) Matsuzawa, S.; Horiguchi, Y.; Nakamura, E.; Kuwajima, I.,
Tetrahedron 1989

, 45, 349. (b) Bergdahl, M.; Lindstedt, E.-L.; Nilsson,

M.; Olsson, T., Tetrahedron 1988, 44, 2055. (c) Bergdahl, M.; Lindstedt,
E.-L.; Nilsson, M.; Olsson, T., Tetrahedron 1989, 45, 535.

13.

Dictionary of Organometallic Compounds

, 2nd ed.; Macintyre, J. E.,

Ed.; Chapman and Hall: New York, 1995; Vol. 1, p 1079.

John N. Haseltine

Georgia Institute of Technology, Atlanta, GA, USA

Avoid Skin Contact with All Reagents