Trimethylchlorosilane modified Clemmensen reduction of metallocenyl ketones: Trapping of aliphatic, olefinic, and pinacolic products
Conference
·
OSTI ID:250119
- Universitaet Innsbruck, Innsbruck (Austria)
The Clemmensen reduction of a carbonyl group to give, in the simplest cases, a methylene unit, is one of the more familiar reactions in organic chemistry. Trimethyl-chlorosilane as a replacement for the proton allows controlled reductive deoxygenation of carbonyl compounds under anhydrous reaction conditions as an alternative to the McMurry dicarbonyl coupling reaction. Aromatic carbonyl compounds with electron-donor substituents are preferred substrates for this reaction to yield symmetrical olefins in good yield. The high donor capacity of metallocenyl groups should especially favor the clean formation of olefins; from the corresponding metallocenyl ketones. In this study, a number of ferrocenyl and ruthenocenyl aldehydes and ketones were treated with Zn and trimethylchlorosilane under controlled reaction conditions. The observed main products include alkanes, alkenes, and silylated pinacols, which have been characterized by spectroscopic methods and by X-ray analyses. The diverse outcome in these reactions, starting from different metallocenyl ketones, is difficult to explain by electronic and steric considerations and indicates a reaction mechanism with different energetically similar pathways.
- OSTI ID:
- 250119
- Report Number(s):
- CONF-9508100--
- Country of Publication:
- United States
- Language:
- English
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