Phenylselenocopper(I)

PhSeCu

[41962-55-4]  · C6H5CuSe  · Phenylselenocopper(I)  · (MW 219.62)

(source of nucleophilic phenylselenide for preparation of lithium alkylphenylselenocuprates and organophosphinecopper(I) phenylselenolate complexes)

Physical Data: mp 150 °C (dec).

Solubility: partially sol cold THF.

Preparative Methods: phenylselenocopper can be prepared by two different procedures (eq 1). In the more straightforward procedure, Benzeneselenol is reacted with copper(I) oxide in ethanol at reflux to yield PhSeCu as a yellow or brown precipitate in 94% yield.1 Similarly, uncharacterized (PhSeCu)n has been prepared from benzeneselenol and Copper(II) Acetate (2:1) in methanol.2 A second type of preparation involves reaction of Bu2Sn(SePh)2 with copper(II) nitrate in methanol;3 an observed byproduct in this reaction is PhSeSePh. The tin reagent is obtained from PhSeH by reaction with Bu2SnCl2. PhSeCu has also been prepared by direct electrochemical oxidation of Diphenyl Diselenide.6

Handling, Storage, and Precautions: selenium reagents should always be used in a fume hood.

Cuprate Reagents.

Lithium alkyl(phenylseleno)cuprates, which are reacted with alkylseleno-substituted vinyl sulfones to effect stereoselective alkylation at the selenium-bearing carbon (eq 2), are prepared by the reaction of PhSeCu with the requisite alkyllithium in THF at 0 °C.1b The cuprates are generated in situ and then treated with the sulfone and warmed to rt.1b,4 Interestingly, these cuprates have afforded superior yields to the traditional cyano and thiophenyl mixed cuprates; the latter reagents also added in a conjugate fashion to give saturated products. Alkyl groups which have been coupled in good yield are Me, i-Pr, n-Bu, s-Bu, t-Bu, and 3-pentyl (67-97%).

Organophosphine Complexes.

A cyclohexylphosphinecopper(I) phenylselenolate complex has been synthesized from (PhSeCu)n to study its 1:1 adduct formation and subsequent stability with SO2 (eq 3).5 Addition of solid tricyclohexylphosphine to an acetonitrile suspension of (PhSeCu)n followed by stirring for 30 min yields the precipitated complex.

Related Reagents.

Phenylthiocopper(I).


1. (a) Osuka, A.; Ohmasa, N.; Suzuki, H. S 1982, 857. (b) Back, T. G.; Collins, S.; Law, K.-W. TL 1984, 25, 1689.
2. Duncan, W. E.; Ott, E.; Reid, E. E. Ind. Eng. Chem. 1931, 23, 381.
3. Macmullin, E. C.; Peach, M. E. JOM 1973, 52, 355.
4. Back, T. G.; Proudfoot, J. R.; Djerassi, C. TL 1986, 27, 2187.
5. Eller, P. G.; Kubas, G. J. JACS 1977, 99, 4346.
6. Kumar, R.; Tuck, D.G. CJC 1989, 67, 127.

William J. Hoekstra

The R. W. Johnson Pharmaceutical Research Institute, Spring House, PA, USA



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