REACTIONS OF (CO)5MNSI(CH3)3 WITH ALPHA-BROMO CARBONYL AND RELATED ORGANIC-COMPOUNDS - FACILE REDUCTIVE SILYLATION
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Reactions of (CO)6MnSi(CH3)3 (1, 1.0-3.0 equiv, 2550 C) with -bromo carbonyl compounds, -(diphenylphosphino)isobutyraldehyde, and -bromo dimethyl acetals and ketals are examined. The -bromo carbonyl compounds are reductively silylated to trimethylsilyl enol ethers in fair to excellent yields. The initial inorganic product is (CO)6MnBr. A mechanism is proposed in which 1 initially silylates the carbonyl oxygen and (CO)5Mn- subsequently abstracts bromine. The phosphino aldehyde is similarly reduced, and the acetals and ketals are converted to methyl enol ethers and CH3OSi(CH3)3. The synthetic utility of these transformations is discussed. 1985, American Chemical Society. All rights reserved.