A new palladium-catalyzed method to prepare pyrroles directly from three basic building blocks-imines, alkynes, and acid chlorides-is described. This approach provides a straightforward method both to prepare pyrroles in one step and to diversify their structure by simple variation of any of the three starting materials. Mechanistic studies suggest that this process occurs via a complex series of eight individual steps, and this is discussed.

A new palladium-catalyzed route to prepare 1,3-oxazolium-5-oxides (i.e., Münchnones) directly from imine, carbon monoxide, and acid chloride building blocks has been developed. This provides a straightforward catalytic synthesis of Münchnones and is amenable to generating a diverse range of products by simple modification of the imine or acid chloride starting materials. Münchnones are vital synthetic intermediates to a variety of heterocyclic and peptide-based molecules. As such, this methodology has been utilized to design a new catalytic synthesis of alpha-amino acid derivatives via a one-pot coupling of imines, carbon monoxide, and acid chloride followed by alcohol. The latter represents the first reported catalytic synthesis of alpha-amino acids directly from imine and carbon monoxide building blocks.

One of the most facile routes to prepare carboxylate‐substituted imidazolines is by the palladium‐catalyzed coupling of an imine, carbon monoxide, and an acid chloride. In this reaction, a peptide unit is constructed and directly incorporated into the heterocyclic core (see scheme).

A new palladium-catalyzed synthesis of 3-amido-substituted beta-lactams is reported. This process involves the one-pot coupling of four components, imines, carbon monoxide, and acid chloride, providing a flexible route to construct this class of heterocycle. The generation of beta-lactams with two different imines can also be accomplished, providing a method to assemble these products with independent control over five separate substituents.

An alternative to nucleophilic chemistry for the construction of α‐substituted amides and amine derivatives from imines is provided by the Stille‐type coupling of imines with organotin reagents and acid chlorides (see scheme). This Pd‐catalyzed reaction is suitable for components with a range of functional groups and has been extended into a four‐component‐coupling reaction with carbon monoxide. dba=dibenzylideneacetone, RT=room temperature.