[89656-96-2]  · C12H20SSi  · 2-(Phenylthio)-2-(trimethylsilyl)propane  · (MW 224.48)

(Peterson alkenation1 and preparation of ketones via 2-lithio-2-(trimethylsilyl)propane2,3)

Physical Data: bp 70-80 °C/0.6 mmHg.

Preparative Method: by reductive lithiation of 2,2-bis(phenylthio)propane followed by trimethylsilylation with Chlorotrimethylsilane.2,3

Purification: by flash chromatography and by Kugelrohr distillation.3

Handling, Storage, and Precautions: use in a fume hood.

Synthesis of Dienes via Peterson Alkenation.

Reductive lithiation of 2-(phenylthio)-2-(trimethylsilyl)propane with Lithium 1-(Dimethylamino)naphthalenide (LDMAN) furnishes 2-lithio-2-(trimethylsilyl)propane, which is an intermediate for Peterson alkenation. The specific example in eq 1 features silicon-directed diene synthesis.1

Synthesis of Ketones.

m-Chloroperbenzoic Acid oxidizes 2-(phenylthio)-2-(trimethylsilyl)propane to the sulfone, which is then converted to the ketone via sila-Pummerer rearrangement (eq 2).3

1. Brown, P. A.; Bonnert R. V.; Jenkins P. R.; Selim, M. R. TL 1987, 28, 693.
2. Cohen, T.; Sherbine, J. P.; Matz, J. R.; Hutchins, R. R.; McHenry, B. M.; Willey, P. R. JACS 1984, 106, 3245.
3. Ager, D. J. JCS(P1) 1986, 183, 195.

Uko E. Udodong

Eli Lilly and Company, Indianapolis, IN, USA

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