Cyanocuprates Convert Carboxylic Acids Directly into Ketones

Carboxylic acids were converted directly in 56-99% yields into methyl, n-butyl, and isopropyl ketones using excess cyanocuprates R2CuLi center dot LiCN. A substrate with a stereocenter alpha to the carboxylic acid was converted into ketones with very little loss of enantiomeric purity. A variety of functional groups were tolerated including aryl bromides. This direct transformation of a carboxylic acid into ketone with minimal tertiary alcohol formation is proposed to involve a relatively stable copper ketal tetrahedral intermediate.