SummaryThis review highlights the development of palladium-catalyzed C–H and N–H functionalization reactions involving indole derivatives. These procedures require unactivated starting materials and are respectful of the basic principle of sustainable chemistry tied to atom economy.

An efficient, direct synthesis of oxazolidinones fused to six-membered heterocyclic rings starting from carbamate-protected aminoalkenes has been developed. This procedure is based on an oxidative palladium(II)-catalyzed reaction performed in the presence of stoichiometric copper chloride, which is determinant to promote the formation of the bicyclic product and prevent the isolation of the monocyclic amination product. Oxazolidinone compounds arise from a domino aminocarboxylation process through the direct intervention of the carbamate oxygen after the initial palladium-promoted transfer of the nitrogen atom on the C=C double bond.

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SummaryIn a simple procedure, the intramolecular hydroarylation of N-propargyl-pyrrole-2-carboxamides was accomplished with the aid of gold(III) catalysis. The reaction led to differently substituted pyrrolo[2,3-c]pyridine and pyrrolo[3,2-c]pyridine derivatives arising either from direct cyclization or from a formal rearrangement of the carboxamide group. Terminal alkynes are essential to achieve bicyclic pyrrolo-fused pyridinones by a 6-exo-dig process, while the presence of a phenyl group at the C–C triple bond promotes the 7-endo-dig cyclization giving pyrrolo-azepines.

2‐Vinyl‐ and 2‐(α‐styryl)quinazolin‐4‐ones have been synthesized by intramolecular gold‐catalyzed hydroamination and palladium‐catalyzed carboamination of anthranilic allenamides, easily prepared by prototropic isomerization of the corresponding propargylamides. These procedures, which lead to N‐Boc‐protected quinazolinones, represent a more flexible alternative to the reported palladium‐catalyzedamination of anthranilic allylamides, achievable only from N‐tosylallylamides.