The key to the general and efficient palladium‐catalyzed formylation of aryl and heteroaryl bromides is the use of the di‐1‐adamantyl‐n‐butylphosphane (cataCXium A) as ligand. Low pressure of the synthesis gas and appropriate choice of the base are also important for high yields (up to 99 %) of a broad range of (hetero)aromatic aldehydes at unprecedented low catalyst concentrations (see scheme; TMEDA= N,N,N′,N′‐tetramethylethylenediamine).

The acid-catalyzed condensation chemistry of simple amides and aldehydes provides a highly prolific source of diverse reactants for irreversible follow-up reactions. Amide-aldehyde mixtures have been successfully employed in multicomponent syntheses of N-acyl alpha-amino acids (via palladium-catalyzed amidocarbonylation) and various cyclohexene, cyclohexadiene, and benzene derivatives (via the amide-aldehyde-dienophile (AAD) reaction).

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