Neutral Trichloroacetylations of Alcohols by Hexachloroacetone

Article abstract of DOI:10.1021/jo00330a028

The addition of simple alcohols in hexachloroacetone (HCA) in the presence of strong hydrogen bond acceptors (e.g., dimethylformamide) results in a high yield of the corresponding trichloroacetate (via a haloform reaction scheme).The trichloroacetylation reactions are carried out under neutral conditions, and the resultant ester can easily be separated from the reaction mixture via extraction/distillation procedures.Kinetic evidence demonstrates that the trichloroacetylation of alcohols by HCA is a stereoselective process, and further studies suggest that the catalytic role of the acceptors is of a hydrogen bonding nature.