Phenyl Trimethylsilyl Selenide

PhSeSiMe3

[33861-17-5]  · C9H14SeSi  · Phenyl Trimethylsilyl Selenide  · (MW 229.28)

(synthesis of benzeneselenol;1a introduction of the phenylseleno function into a variety of oxygen-containing compounds2-4,6)

Physical Data: bp 92-93 °C/5 mmHg. 1H NMR (CDCl3) d 0.35 (Me3Si); 13C NMR (CDCl3) d 1.49 (Me3Si).

Solubility: sol benzene, Et2O, THF, MeCN.

Preparative Methods: conveniently prepared by the reduction of Diphenyl Diselenide with Sodium in THF, followed by silylation of thus formed PhSeNa with Chlorotrimethylsilane.1a,b In a small scale reaction, silylation of PhSeLi, which can be prepared in situ from metallic Selenium and Phenyllithium in THF, is alternatively utilized.1c

Purification: distillation under reduced pressure.

Handling, Storage, and Precautions: although phenyl trimethylsilyl selenide isolated as a colorless liquid is somewhat sensitive to atmospheric moisture, it can be handled conveniently using syringe techniques and can be stored indefinitely under dry nitrogen (or argon). Use in a fume hood.

Reaction with Aldehydes and Ketones.

Phenyl trimethylsilyl selenide does not react with carbonyl compounds at 25 °C or on heating. However, use of Aluminum Chloride as catalyst results in selective formation of selenoacetals, whereas the copresence of zinc halide in place of AlCl3 leads to O-(trimethylsilyl) monoselenoacetals,2a-d which can be utilized as a-siloxy radical precursors (eq 1).2e

Reaction with Acetates and Lactones.

In the presence of a catalytic amount of Zinc Iodide, alkyl acetates and lactones react with phenyl trimethylsilyl selenide to afford alkyl phenyl selenides and o-(phenylseleno)carboxylic acids, respectively (eq 2).3

Reaction with a,b-Unsaturated Carbonyl Compounds.

Conjugate addition of phenyl trimethylsilyl selenide to a,b-unsaturated aldehydes and ketones has been attained by using Triphenylphosphine,2c Zinc Chloride,2c or Trimethylsilyl Trifluoromethanesulfonate4 as the catalyst. Combination of this reaction with selenoxide elimination5 provides a one-pot procedure for a-alkoxyalkylation of a,b-unsaturated ketones (eq 3).

Reaction with Cyclic Ethers.

Ring opening of epoxides, oxetanes, and tetrahydrofurans with phenyl trimethylsilyl selenide takes place in the presence of ZnI2 to provide b-, g-, and d-siloxyalkyl phenyl selenides, respectively, in good yields (eq 4).6

Miscellaneous.

Introduction of a phenylseleno function into organic molecules has also been attained by the reaction of phenyl trimethylsilyl selenide with organic halides.7 Palladium-catalyzed addition of PhSeSiMe3 to arylacetylenes takes place regio- and stereoselectively to give b-silyl substituted vinylic selenides (eq 5).8 PhSeSiMe3 serves as a mild reducing agent for deoxygenation of sulfoxides, selenoxides, and telluroxides.9

Phenyl Trimethylsilyl Telluride.

PhTeSiMe3 is synthesized by the reaction of Me3SiCl with PhTeLi,10a PhTeNa,10b or PhTeMgBr,10c and is purified by distillation (bp 77-79 °C/2 mmHg). It can be stored as a 2.5 M hexane solution in a Schlenk flask. Like PhSeSiMe3, PhTeSiMe3 reacts with cyclic ethers and lactones to give ring-opened products.10b Upon treatment with MeOH, benzenetellurol is formed in situ.10d

Related Reagents.

Benzeneselenol; Bis(trimethylsilyl) Selenide.


1. (a) Miyoshi, N.; Ishii, H.; Kondo, K.; Murai, S.; Sonoda, N. S 1979, 300. (b) Detty, M. R.; Seidler, M. D. JOC 1981, 46, 1283. (c) Drake, J. E.; Hemmings, R. T. JCS(D) 1976, 1730.
2. (a) Dumont, W.; Krief, A. AG(E) 1977, 16, 540. (b) Clarembeau, M.; Cravador, A.; Dumont, W.; Hevesi, L.; Krief, A.; Lucchetti, J.; Van Ende, D. T 1985, 41, 4793. (c) Liotta, D.; Paty, P. B.; Johnston, J.; Zima, G. TL 1978, 5091. (d) Detty, M. R. TL 1979, 4189. (e) Keck, G. E.; Tafesh, A. M. SL 1990, 257.
3. Miyoshi, N.; Ishii, H.; Murai, S.; Sonoda, N. CL 1979, 873.
4. Suzuki, M.; Kawagishi, T.; Noyori, R. TL 1981, 22, 1809.
5. Reich, H. J. Oxidation in Organic Chemistry; Trahanovsky, W., Ed.; Academic: New York, 1978; Part C, p 1.
6. (a) Miyoshi, N.; Kondo, K.; Murai, S.; Sonoda, N. CL 1979, 909. (b) Miyoshi, N.; Hatayama, Y.; Ryu, I.; Kambe, N.; Murai, T.; Murai, S.; Sonoda, N. S 1988, 175.
7. (a) Paquette, L. A.; Lagerwall, D. R.; Korth, H.-G. JOC 1992, 57, 5413. (b) Kato, S.; Yasui, E.; Terashima, K.; Ishihara, H.; Murai, T. BCJ 1988, 61, 3931.
8. Ogawa, A.; Sonoda, N. J. Synth. Org. Chem. Jpn. 1993, 51, 815.
9. Detty, M. R. JOC 1979, 44, 4528.
10. (a) Drake, J. E.; Hemmings, R. T. IC 1980, 19, 1879. (b) Sasaki, K.; Aso, Y.; Otsubo, T.; Ogura, F. TL 1985, 26, 453. (c) Jones, C. H. W.; Sharma, R. D. JOM 1984, 268, 113. (d) Ohira, N.; Aso, Y.; Otsubo, T.; Ogura, F. CL 1984, 853.

Akiya Ogawa

Osaka University, Japan



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