Synthetic Design of Carbonyl-Group-Containing Compounds Based on C−O Bond Cleavage Promoted by Pd Complexes

On the basis of fundamental studies on elementary processes involving allyl−O and acyl−O bond cleavages, various new catalytic processes to convert carboxylic acid derivatives have been realized. The new processes include 1) carbonylation of allyl formates to β,γ-unsaturated acids, 2) amination, alkylation, and carbonylation of allylic alcohols, 3) aldehyde synthesis by hydrogenation of carboxylic anhydrides and carboxylic acids, 4) ketone synthesis by combination of the C−O bond cleavage with transmetallation by organoboronic acids. The processes described here have advantages over the conventional ones in that they are more atom-efficient and halogen-free in realizing the syntheses of a variety of carbonyl-containing compounds under mild conditions.