Reactions of (CO)5MnSi(CH3)3 with α-Bromo Carbonyl and Related Organic Compounds. Facile Reductive Silylation

Article abstract of DOI:10.1021/jo00218a030

Reactions of (CO)5MnSi(CH3)3 (1, 1.0-3.0 equiv, 25-50 deg C) with α-bromo carbonyl compounds, α-(diphenylphosphino)isobutyraldehyde, and α-bromo dimethyl acetals and ketals are examined.The α-bromo carbonyl compounds are reductively silylated to trimethylsilyl enol ethers in fair to excellent yields.The initial inorganic product is (CO)5MnBr.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