Cyclopalladated phosphine free pyrazole complexes 1 and benzothiazole complexes 2 are excellent catalysts for the Heck vinylation of aryl iodides and termolecular queuing cascades, leading to turnover numbers of > 10 6 in some cases, at moderate temperatures; these catalysts show high thermal stability and are not sensitive to moisture and air.

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Two paths diverge: Four‐component cascades that involve the cycloaddition of azomethine ylides, azomethine imines, or nitrones generated in situ, coupled with allene incorporation, give rise to five new bonds, two rings, and two to four stereocenters through two possible pathways (see picture for an example).

We herein describe a novel palladium catalysed three-component cascade process involving carbonylation of an aryl iodide to generate an acyl palladium(II) species that is intercepted by a primary aliphatic or aromatic amine, amide, or sulfonamide followed by intramolecular Michael addition to furnish N-substituted isoindolinones in good yield. Overall, the cascade results in the formation of one C—C and two C—N bonds, one ring and one stereocentre.Key words: isoindolinone, palladium, cascade, amidation, sulfonamidation.