Sodium Phenanthrenide

[96229-74-2]  · C14H10Na  · Sodium Phenanthrenide  · (MW 201.23)

(dehalogenation of vicinal dichlorides1)

Solubility: sol THF

Preparative Method: prepared by adding 1.0 equiv of Sodium to a solution of 1.1 equiv of phenanthrene in dry THF. The resulting dark-green solution is stirred for 18 h at rt.1

Handling, Storage, and Precautions: should be used as prepared, under anhydrous conditions; the dry solid and solutions are flammable.

Dehalogenation Agent.

Sodium phenanthrenide is a useful reagent for the dehalogenation of vicinal dichlorides, resulting in the formation of alkenes. An isomeric mixture of cis- and trans-exo,exo-3,4-dichlorotetracyclo[,5.07,10]dodeca-8,11-diene is easily converted to exo,exo-tetracyclo[,5.07,10]dodecatriene in the presence of sodium phenanthrenide in THF (eq 1).1

In addition to sodium phenanthrenide, disodium phenanthrenide,2 zinc metal,3 chromium dichloride,4 titanium trichloride/lithium aluminum hydride,5 sodium sulfide nonahydrate,6 and activated nickel complexes7 have also been employed in dehalogenations of 1,2-dihalides.

Related Reagents.

Chromium(II) Chloride; Disodium Phenanthrenide; Lithium 4,4-Di-t-butylbiphenylide; Lithium Naphthalenide; Potassium Naphthalenide; Sodium Anthracenide; Sodium Naphthalenide; Sodium Sulfide; Titanium(III) Chloride-Lithium Aluminum Hydride; Zinc.

1. (a) Paquette, L. A.; Stowell, J. C. JACS 1971, 93, 5735. (b) Paquette, L. A.; Stowell, J. C. TL 1969, 47, 4159.
2. (a) Wiberg, K. B.; Uberson, R. W. JOC 1972, 37, 3827. (b) McDonald, R. N.; Frichy, D. G. JACS 1968, 90, 5315. (c) Vogel, E.; Kieter, H. AG(E) 1964, 3, 442.
3. (a) Dailey, W. P.; Correa, R. A.; Harrison, E.; Lemal, D. M. JOC 1989, 54, 5511. (b) Iyodo, M. TL 1985, 26, 3719. (c) Attenburrow, J. JCS 1961, 4547.
4. (a) Robinson, C. H. JACS 1959, 81, 2191. (b) Bowers, A. JACS 1960, 82, 4001. (c) Kerb, U.; Wiechert, R. CB 1962, 95, 2956. (d) Bowers, A. JACS 1960, 82, 4007.
5. Olah, G. A.; Prakash, G. K. S. S 1976, 607.
6. Fukunaya, K.; Yamaguchi, H. S 1981, 879.
7. (a) Iyoda, M.; Kitami, S.; Yamauchi, T.; Oda, M. CL 1986, 12, 2113. (b) Iyoda, M.; Sakaitani, M.; Kojima, A.; Oda, M. TL 1985, 26, 3719.

Nick Nikolaides

3M Pharmaceuticals, St. Paul, MN, USA

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